Thermoplastic poly(urethane-co-carbonate) based on (hetero)aromatic urethane diol prepolymers

Abstract

A thermoplastic poly(urethane-co-carbonate) based on aromatic diisocyanate and a process for the preparation thereof are described. The poly(urethane-co-carbonate) has a weight-average molecular weight of at least 40,000 g / mol and a defined ratio of carbonate groups to urethane groups.

Description

[0001] 2024PF30150a

[0002] - 1 -

[0003] Thermoplastic polyurethane-co-carbonate) based on (hetero)aromatic urethanediol prepolymers

[0004] The present invention relates to thermoplastic poly(urethane-co-carbonate)s based on aromatic diisocyanates and a process for their production. Urethanediol prepolymers, which are also part of the present invention, are obtained in the production process.

[0005] Aromatic polycarbonates are known for their good mechanical and optical properties, heat resistance, and weather resistance. However, the presence of aromatic groups also results in some properties that could be improved, such as transmission, birefringence, and yellowing tendencies. Furthermore, depending on the manufacturing process, a significant amount of phenol is produced as condensate, which requires technically complex collection and processing. Aliphatic polycarbonates exhibit improved properties in the aforementioned areas requiring further refinement, as well as in chemical resistance; however, they generally have lower glass transition temperatures and consequently lower heat resistance.It would be desirable to be able to use polymers that combine the positive properties of aromatic polycarbonates and aliphatic polycarbonates, while avoiding the negative properties and generating as little phenol as possible during production.

[0006] In EP 2 883 898 Al, an aliphatic polycarbonate is blended with a polyurethane. The formation of an IPN (interpenetrating polymer network) improves the mechanical properties of the aliphatic polycarbonate. The aliphatic polycarbonate is either polypropylene carbonate or polyethylene carbonate. It therefore contains linear aliphatic structures, which typically result in low glass transition temperatures (approximately 25–45 °C).

[0007] WO 2013 / 016331 A2 describes a polyurethane composition comprising an aliphatic polycarbonate structure. This structure also contains linear ethylene oxide or propylene oxide chains and has a number-average molecular weight of less than 20,000 g / mol. Depending on the molecular weight, these polyols can be liquid or crystalline at room temperature. The polyols containing the carbonate groups are then reacted with aromatic diisocyanates. The 2024PF30150a described in WO 2013 / 016331 A2

[0008] - 2 -

[0009] Polymers typically exhibit thermal stability and susceptibility to oxidation that require improvement.

[0010] EP 1 700 877 Al describes poly(urethane carbonate) polyols obtained using aliphatic linear diols and aliphatic diisocyanates. A molar ratio of diol to diisocyanate of at least 4:1 is always used. The resulting OH-terminated prepolymer is then reacted with diphenyl carbonate along with the unreacted excess diol to yield the poly(urethane carbonate) polyol with a relatively low molar mass of approximately 1000 to 2000 g / mol (indicated by the OH numbers). The resulting polyols exhibit glass transition temperatures below 0 °C. They are first reacted with an aromatic diisocyanate to form a prepolymer and then processed into a castable elastomer by adding a linear diol. Since this document concerns the production of castable elastomers, the glass transition temperatures of the polyols are not the focus.adapted to the areas required for cast elastomers. These differ significantly from the preferred areas for thermoplastic polycarbonate compositions or comparable polymers.

[0011] Based on the prior art, the objective was therefore to overcome at least one, preferably several, and more preferably all disadvantages of the prior art. In particular, the objective of the present invention was to provide a thermoplastic polymer which has glass transition temperatures of at least 70 °C, preferably at least 80 °C, and more preferably at least 90 °C. By incorporating aliphatic starting materials, the thermoplastic polymer should exhibit good optical properties (especially transparency). The thermoplastic polymer should preferably also exhibit high heat resistance (despite the use of aliphatic components). Equally preferably, the thermoplastic polymer should be processable using the plasticizing methods commonly used for aromatic polycarbonate (e.g., injection molding, (co)extrusion, blow molding, thermoforming).It is particularly advantageous if the thermoplastic polymer is amorphous. Preferably, the thermoplastic polymer should exhibit good mechanical properties, for example, properties comparable to aromatic polycarbonates. Most preferably, the thermoplastic polymer should exhibit at least ductile fracture at room temperature. The polymer should also be as cost-effective to produce as possible. 2024PF30150a.

[0012] - 3 -

[0013] The as-yet-unpublished European patent application No. 23217149.6 proposes a solution: a thermoplastic poly(urethane-co-carbonate) based on at least cycloaliphatic diols and cycloaliphatic diisocyanates. However, the groups introduced into the polymer by the diisocyanate always contain at least a cycloaliphatic component. It has now been shown, however, that exclusively aromatic, including heteroaromatic, diisocyanates can also be used, which likewise leads to an attractive group of polymers. Aromatic diisocyanates exhibit higher reactivity than aliphatic diisocyanates, which typically results in faster reaction times and thus more efficient production processes. Consequently, smaller amounts of catalyst could also be used.The thermoplastic poly(urethane-co-carbonate)s according to the invention preferably also exhibit good mechanical properties, specifically generally higher stiffness and strength, higher dynamic load capacity, higher abrasion resistance, and higher wear resistance compared to poly(urethane-co-carbonate)s based on aliphatic diisocyanates. Compared to poly(urethane-co-carbonate)s based on aliphatic diisocyanates, the thermoplastic poly(urethane-co-carbonate)s according to the invention also preferably exhibit increased hardness, increased temperature resistance at high temperatures, particularly due to higher glass transition temperatures, and better dimensional stability, which, without being bound to this theory, is presumably due to the formation of hard segments in the polymers by the aromatic diisocyanates.Typically, the thermoplastic poly(urethane-co-carbonate)s produced according to the invention also exhibit improved processability. Aromatic diisocyanates such as MDI and TDI are usually also readily available and cost-effective, more so than aliphatic diisocyanates, leading to more economical production processes.

[0014] The invention thus relates to a thermoplastic poly(urethane-co-carbonate) comprising structures of formulas (I) and (II), wherein

[0015] (I), where each R 1 in formula (I) each independently represents an aliphatic group with 4 to 18 carbon atoms, which has at least one cycle and this cycle may optionally contain at least one heteroatom, and 2024PF30150a

[0016] - 4 - where each R 2Formula (II) each independently represents a bridging aromatic structure with 6 to 18 carbon atoms, wherein the wavy lines in formulas (I) and (II) each represent the connection of the structures of formulas (I) and (II) to the chain of poly(urethane-co-carbonate), and wherein at least a part of the structures of formulas (I) and (II) are each directly linked to each other to form a urethane group, and at least a further part of the structures (I) are directly linked to at least one further structure of formula (I) to form a carbonate group, characterized in that the thermoplastic poly(urethane-co-carbonate) has > 1 mol% to < 99 mol% carbonate groups, based on the sum of the carbonate and urethane groups in the poly(urethane-co-carbonate), wherein the mol% of carbonate and urethane groups are determined by 13C-NMR spectroscopy is determined, and that the thermoplastic poly(urethane-co-carbonate) has a weight average molar mass of at least 40,000 g / mol and that the thermoplastic poly(urethane-co-carbonate) does not have structures of the general formula exhibits structures where R is not an aromatic group. In formula (II*), the wavy lines also represent the attachment of the structure to the poly(urethane-co-carbonate) chain.

[0017] The structure of formula (I) is preferably obtained by using an aliphatic, bilaterally primary diol, which has at least one cycle that may contain a heteroatom. The structure of formula (II) is preferably obtained by using an aromatic diisocyanate with 6 to 18 carbon atoms. According to the invention, "aromatic structures" also include heteroaromatic structures.

[0018] It is understood that the thermoplastic poly(urethane-co-carbonate) according to the invention is not one as described in claim 1 of European patent application No. 23217149.6, because the thermoplastic poly(urethane-co-carbonate) described therein has 2024PF30150a

[0019] - 5 - always contains at least units obtained by using a (hetero)cycloaliphatic diisocyanate. The thermoplastic poly(urethane-co-carbonate) according to the present invention therefore also contains no units of the formula on, where R represents a bridging aliphatic structure with 6 to 18 carbon atoms, wherein this bridging structure has at least one cycle and this cycle may optionally contain at least one heteroatom, and wherein the bridging structure is connected to the nitrogen atoms shown in structure (II*) via a secondary or tertiary carbon atom.

[0020] The thermoplastic poly(urethane-co-carbonate)s according to the invention are amorphous. This amorphous nature, among other factors, gives them good optical properties. In particular, the poly(urethane-co-carbonate)s according to the invention are transparent. Preferably, the term "transparent" within the meaning of the present invention is to be understood as meaning that injection-molded sheets have a light transmission in the visible range of the spectrum (380 to 780 nm, transmittance TVIS) of at least 20%, preferably at least 50%, more preferably at least 70%, particularly preferably at least 80%, and most preferably at least 88%, determined according to DIN ISO 13468-2:2006 (D65, 10°, layer thickness of the sample sheet: 4 mm). Equally preferably, these injection-molded sheets also have a turbidity of less than 30%, more preferably less than 20%, particularly preferably less than 10%, particularly preferably less than 7%, and most preferably less than 3%, determined according to ASTM D1 003:2013.This refers in particular to injection-molded plates that exhibit visual transparency, i.e., that show the background.

[0021] Likewise, the thermoplastic poly(urethane-co-carbonate)s of the present invention, because they are amorphous, can be used in particular in plasticizing methods known for aromatic polycarbonates (e.g., injection molding, (co)extrusion, blow molding, thermoforming), since they exhibit "thermoplastic" properties known to those skilled in the art. According to the invention, the term "thermoplastic" preferably refers to a polymer that can be deformed within a temperature range, particularly above room temperature, especially preferably at temperatures > 50 °C, and most preferably at temperatures > 90 °C. This deformation is preferably reversible. 2024PF30150a

[0022] - 6 -

[0023] In particular, the term "thermoplastic" is preferably used according to the invention to distinguish it from thermoset and / or elastomeric polymers. Such thermoset and / or elastomeric polymers exhibit physical cross-linking of the individual polymer chains, which results in deformation (exceeding the elastic range) being irreversible. Such polymers cannot be deformed / shaped by conventional plasticizing processes. The poly(urethane-co-carbonate) according to the invention offers the advantage that its properties are similar to those of conventional aromatic polycarbonates. Because the poly(urethane-co-carbonate)s according to the invention are amorphous, they exhibit no relevant shrinkage, preferably less than 1% in any spatial direction. The term "shrinkage" is familiar to those skilled in the art in connection with polymers, especially crystalline polymers.The term preferably refers to the effect that, as a polymer melt cools, the formation of crystals leads to a reduction in volume. This results in a decrease in the volume and dimensions of an injection-molded part compared to the original shape. This can be avoided by using an amorphous polymer. While crystalline polymers can be used in extrusion or injection molding processes, shrinkage must always be considered for the resulting molded part. Therefore, aromatic polycarbonates cannot simply be replaced by crystalline polymers in standard plasticizing processes.

[0024] Furthermore, the thermoplastic poly(urethane-co-carbonate)s of the invention exhibit good mechanical properties, for example, at least ductile fracture at room temperature. Thus, the thermoplastic poly(urethane-co-carbonate)s of the invention possess a particularly good property profile, which is comparable to, and preferably better than, that of classic aromatic polycarbonates (for example, based on bisphenol A). In particular, in addition to the good mechanical properties, the thermoplastic poly(urethane-co-carbonate)s of the invention also exhibit good chemical resistance (especially hydrolysis resistance), good transmission, good birefringence, and a low tendency to yellow.

[0025] The inventive thermoplastic poly(urethane-co-carbonate) has both urethane and carbonate groups. It is not excluded that the inventive poly(urethane-co-carbonate) also has further functional groups that differ from the structures of formulas (I) and (II). However, it is preferred that the inventive poly(urethane-co-carbonate) has no ether groups and / or no ester groups. Preferably, the inventive poly(urethane-co-carbonate) 2024PF30150a

[0026] - 7 - thus, no ether groups. In particular, the poly(urethane-co-carbonate) according to the invention preferably has no linear ether groups. This preferably means that the poly(urethane-co-carbonate) according to the invention does not comprise polyethylene oxide and / or polypropylene oxide segments. Equally preferably, and in particular more preferably, the poly(urethane-co-carbonate) according to the invention also has no ester groups. The absence of such groups is preferred according to the invention because, according to the invention, polyether polyols and / or polyester polyols are preferably not used in the production of the poly(urethane-co-carbonate) according to the invention. It is understood that the components used may contain common impurities, which, for example, originate from their manufacturing processes. Corresponding impurities and resulting structures may therefore also be found in the poly(urethane-co-carbonate).Therefore, the inventive poly(urethane-co-carbonate) may also contain traces of ether and / or ester groups. However, it is preferred to use components that are as pure as possible. It is further understood that these impurities may also be present in a closed formulation of the compounds used.

[0027] It is also preferred that no structures are included which arise when a structure of formula (II) is directly linked to a structure of formula (II). This would result in hydroxyl groups.

[0028] It is also apparent to a person skilled in the art that further functional groups can be incorporated into the inventive poly(urethane-co-carbonate) by means of special monofunctional chain breakers.

[0029] Particularly preferably, the poly(urethane-co-carbonate) according to the invention essentially comprises urethane and carbonate groups for linking formulas (I) and (II) together. These structures form the essential part of the polymer chain of the poly(urethane-co-carbonate). For example, by linking at least a part of the structures (I) with at least one other structure of formula (I), a structure of formula (IA) can be formed directly: 2024PF30150a

[0030] - 8 -

[0031] This refers to R 1 for the meanings given with regard to formula (I) also in all preferences. It is evident to the person skilled in the art that a carbonate group is formed by the direct combination of at least some of the structures of formula (I) with at least one further structure of formula (I).

[0032] Likewise, by combining at least part of the structures of formula (I) and (II) directly with each other, a structure of formula (IIA) can be formed:

[0033] This involves R 1 and R 2 The meanings given with respect to formula (I) and (II) also apply in all preferences. It is evident to a person skilled in the art that a urethane group is formed by the direct combination of at least some of the structures of formula (I) with (II).

[0034] The structures of formulas (IA) and (IIA) are preferably statistically distributed in the poly(urethane-co-carbonate) according to the invention. This applies in particular if further structures are present which differ from the structures of formulas (I) and (II) / (IA) and (IIA).

[0035] The inventive poly(urethane-co-carbonate) is preferably obtained by the inventive process described in more detail below. First, diols are reacted with aromatic diisocyanates having 6 to 18 carbon atoms. Subsequently, the resulting prepolymer is reacted with a carbonyl source. This process essentially yields urethane and carbonate groups. It is apparent to those skilled in the art that further functional groups can also be incorporated into the poly(urethane-co-carbonate) by using specific diols and / or diisocyanates. However, according to the invention, only aromatic diisocyanates are used. Furthermore, the urethane and carbonate groups constitute the essential part of the functional groups in the polymer chain of the poly(urethane-co-carbonate).Particularly preferably, this means that the functional groups of the poly(urethane-co-carbonate)s consist of at least 80 mol%, particularly preferably at least 90 mol%, most preferably at least 98 mol% of the functional groups “urethane” and 2024PF30150a.

[0036] - 9 -

[0037] “Carbonate”, where the mol% preferably refers to all functional groups which have heteroatoms.

[0038] According to the invention, the poly(urethane-co-carbonate) comprises structures of formulas (I) and (II). This does not preclude the presence of other structures, particularly between the urethane groups and / or carbonate groups, in the poly(urethane-co-carbonate) according to the invention. These could be introduced, for example, by the use of further diols and / or further diisocyanates, provided the latter are aromatic. However, it is preferred that the poly(urethane-co-carbonate) according to the invention consists essentially of the structures of formulas (I) and (II). It is evident to those skilled in the art how structures (I) and (II) are related, in particular that structures (IA) and (IIA) are included. In particular, it is preferred that the poly(urethane-co-carbonate) according to the invention comprises at least 50 wt.%, preferably at least 75 wt.%, particularly preferably at least 80 wt.%, and most preferably at least 90 wt.%.-% and, in particular, preferably at least 95 wt.% consists of the structures of formulas (I) and (II). Here too, it is evident to a person skilled in the art how structures (I) and (II) are related, in particular that structures (IA) and (IIA) are included.

[0039] According to the invention, the poly(urethane-co-carbonate) comprises structures of formula (I)

[0040] (I), where each R 1 In formula (I), each represents an aliphatic group with 4 to 18 carbon atoms, which has at least one cycle and wherein this cycle may optionally contain at least one heteroatom, preferably oxygen, and wherein the wavy lines in formula (I) represent the connection of the structure of formula (I) to the chain of poly(urethane-co-carbonate). It is evident that if R 1If it has more than one cycle, one or more of the 4 to 18 carbon atoms may also be part of two cycles.

[0041] R 1 is defined as an "aliphatic group with 4 to 18 carbon atoms, which has at least one cycle and this cycle may optionally contain at least one heteroatom". R 1 It thus includes “cycloaliphatic” and “heterocycloaliphatic groups”. 2024PF30150a

[0042] - 10 -

[0043] "Cycloaliphatic" within the meaning of the present invention preferably means that the group consists only of carbon atoms and hydrogen atoms. In this and elsewhere, "cycloaliphatic" is preferably understood to mean a group which is a cycloalkylene group. "Cycloalkylene" preferably means that it is a bridging cycloalkane structure from which two hydrogen atoms have been removed from different carbon atoms. It is not excluded that the bonding to the oxygen atoms shown in formula (I) occurs via linear alkylene groups, as long as the defined total number of carbon atoms is present and the overall structure of R 1at least one cycle. The two carbon atoms from which the two hydrogen atoms have been removed can be arbitrary, i.e., any part of the cycle or of the linear alkylene group, if present. Furthermore, according to the present invention, the cycloalkylene group can also be connected to at least one other cycloaliphatic ring via a bridging structure or condensed. A cycloaliphatic group can also have one or more double bonds. The number of carbon atoms of the aliphatic group R 1 The number of carbon atoms here and at all other points where the polymer, the process and the prepolymer are described is preferably 4 to 12, more preferably 6 to 10.

[0044] According to the invention, “heterocycloaliphatic” preferably means, in contrast to “cycloaliphatic”, that at least one cycle of the respective group as such is not only formed by bonded carbon atoms, but that at least one of the carbon atoms in the cycle is replaced by a heteroatom, preferably nitrogen, oxygen, sulfur or phosphorus, wherein the heterocycloaliphatic group preferably comprises oxygen or nitrogen, particularly preferably oxygen, as a heteroatom.

[0045] R is preferred 1 for a C4 to cis-cycloalkylene group.

[0046] In the context of the present invention, the term “alkylene” or “alkylene group” preferably refers, unless otherwise specified, to a bridging alkane structure from which two hydrogen atoms have been removed from different carbon atoms. In this context, 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 need not be. 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 connected to the rest of the molecule via two 2024PF30150a

[0047] - 11 -

[0048] Single bonds are involved. Preferably, the alkylene group comprises methylene, ethylene, n-propylene, isopropylene, 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-Ethyl-1-methylpropylene, 1-Ethyl-2-methylpropylene, 1-Ethyl-2-methylpropylene, and the like. The selection of these structures may be limited if the number of carbon atoms is defined differently within the scope of the present invention.

[0049] The preferred R 1in formula (I), (IA), (IIA) or also in the formulas (III) and (III) shown later, represented by formula (1) or formula (2), where the positions marked with the stem in formulas (1) and (2) are the positions where the CH2 groups shown in formulas (I), (IA), (IIA), and (III) and (III) shown later are located.

[0050] Formula (I) is particularly preferred when represented by the following formulas (II) or (12): where the wavy lines in formula (II) and formula (12) respectively represent the connection of the structures of formulas (II) and (12) to the poly(urethane-co-carbonate) chain. Formula (II) is most preferably based on 1,4-cyclohexanedimethanol.

[0051] It is understood that the thermoplastic poly(urethane-co-carbonate) according to the invention can also comprise several of these structures (1) and (2) or (II) and (12), since different diols, i.e., diol mixtures, can be used. 2024PF30150a

[0052] - 12 -

[0053] It is understood that such compounds can exist in the cis, trans, or a mixture of cis and trans forms. For example, the diol of formulas (1a), (1) is preferably used in the / ram form or as a mixture of cis and trans forms.

[0054] The poly(urethane-co-carbonate) according to the invention can, in addition to the structures of formula (I), also comprise at least one further structure of formula (li): where each R 6in formula (li) represents an aliphatic alkylene group having 4 to 20, preferably 5 to 18, particularly preferably 6 to 16 carbon atoms, which may be linear or branched or may have at least one cycle, wherein the at least one cycle may have at least one heteroatom, and wherein R 6 , if R 6at least one cycle is incorporated into the structure (li) not via a C Ff group, but preferably via a secondary carbon atom directly linked to the oxygen, and wherein the wavy lines in formula (li) each represent the connection of the structure of formulas (li) to the chain of poly(urethane-co-carbonate). These structures of formula (li) can be at least partially directly linked to another structure of formula (li) by forming a carbonate group, or at least partially linked to a structure of formula (I). Likewise, the structures of formula (li) can be at least partially linked to a structure of formula (II) by forming a urethane group. Preferably, the structure of formula (li) is statistically distributed in the poly(urethane-co-carbonate) according to the invention.However, the poly(urethane-co-carbonate) according to the invention most preferably does not comprise a structure of formula (li).

[0055] However, if an additional structure of formula (li) exists, it is particularly preferably at least one further structure of formula (lia) to (lid) 2024PF30150a

[0056] - 13 -

[0057] (lid), where the wavy lines in formula (lia) to (lid) each represent the connection of the structure of the formulas into the chain of poly(urethane-co-carbonate).

[0058] The amount of the further structure of formula (li) or of the particularly preferred structures (lia) to (lid) in the poly(urethane-co-carbonate) according to the invention, if such a structure is included, is preferably selected such that the resulting glass transition temperature of the poly(urethane-co-carbonate) remains > 70 °C. Additionally, ductile fracture should be present at least at room temperature. Preferably, the poly(urethane-co-carbonate) according to the invention contains at most 75 mol%, more preferably at most 60 mol%, even more preferably at most 40 mol%, even more preferably at most 25 mol%, particularly preferably at most 10 mol%, and most preferably at most 5 mol% of the further structure of formula (li) or of the preferred structures (lia) to (lid) with respect to the sum of the structures (li) (or (lia) to (lid)) and the structures (I).It is evident to a person skilled in the art that the expression “at most” includes “0 mol-%”, as it refers to optional further structures of 2024PF30150a.

[0059] - 14 -

[0060] Formula (li) is involved. Most preferably, no further structure of formula (li) is present, thus 0 mol-%. However, if at least one structure of formula (li) or of a preferred structure of formulas (lia) to (lid) is present, then the expression "at most" in this context means that more than 0 mol-% is present.

[0061] Preferably, however, the poly(urethane-co-carbonate) according to the invention does not contain structures of formula (li), in which R 6 represents a -CFFCFhCFhCFh group.

[0062] According to the invention, the poly(urethane-co-carbonate) further comprises structures of formula (II) where each R 2in formula (II) each independently represents a bridging aromatic structure with 6 to 18, preferably 7 to 13 carbon atoms, and wherein the wavy lines in formula (II) each represent the connection of the structures of formula (II) to the chain of poly(urethane-co-carbonate).

[0063] According to the invention, "aromatic" preferably refers to a group comprising at least one cycle of directly bonded carbon atoms with conjugated double bonds. All atoms of the cycle are sp 2 -hybridized. The electrons are delocalized and obey Hückel's rule.

[0064] According to the invention, the term "aromatic group" also includes "heterocyclic aromatic" groups. A "heterocyclic aromatic group" is preferably understood to be a group in which, in addition to carbon atoms, at least one heteroatom forms the at least one cycle that has conjugated double bonds. The heteroatom is preferably nitrogen, oxygen, sulfur, or phosphorus.

[0065] An aromatic group is also present if the group has at least one aromatic cycle, but the isocyanate groups are not directly attached to it, but via another group, in particular an alkylene group.

[0066] Preferably, the bridging structure R is connected 2 to the nitrogen atoms shown in structure (II) via a ring carbon atom of an aromatic cycle. 2024PF30150a

[0067] - 15 -

[0068] It goes without saying that R 2 may also contain at least one heteroatom. Preferably, R 2 However, no heteroatom is present.

[0069] R is preferred 2 for an aromatic group selected from the following structures (3) to (6): where each R 3 in formula (3) independently represents a methyl or ethyl group, p represents 0, 1, or 2, and q represents 0 or 1, and each R 3 in formula (4) independently represents a methyl or ethyl group and p represents 0, 1, or 2 and d represents 0 or 1 independently.

[0070] R is especially preferred 2 for an aromatic group selected from the following structures: where the positions marked with the stem in formulas (3i) and (4i) are the positions where the nitrogen atoms shown in formulas (II), (IIA), and (III) and (III) shown later are located, respectively. 2024PF30150a

[0071] - 16 -

[0072] It is understood that the thermoplastic poly(urethane-co-carbonate) according to the invention can also simultaneously comprise two or more of these structures, for example structures (3) and (4), since different diisocyanates, i.e. diisocyanate mixtures, can be used.

[0073] The thermoplastic poly(urethane-co-carbonate) does not exhibit structures of the general formula (II*) all structures of the general formula (II*) of the poly(urethane-co-carbonate) according to the invention are thus represented by structures in which R is aromatic, preferably R = R 2is, which is a mixture of different R 2 can act. Accordingly, only aromatic diisocyanates are used as diisocyanates in the production of poly(urethane-co-carbonate) via diisocyanates and diols. It is understood that (unintentionally) small amounts of structures (II*) may also be present as "impurities" where R is not aromatic, which may have arisen, for example, due to impurities.

[0074] In particular, the inventive poly(urethane-co-carbonate) preferably comprises structures of formula (II) and / or (12) and structures of formula (II), in which R 2This is represented by a structure of formula (3), where p = 0 and q = 1. Particularly preferably, the structure of formula (3) with p = 0 and q = 1 can be a mixture of different structures. A mixture of 4,4'- and 2,4'- and optionally 2,2'- isomers is preferred. Furthermore, a mixture in which at least 80 mol% of the structures are 4,4'-isomers and the remainder are 2,4'- or 2,2'-isomers is preferred.

[0075] It is preferred that the thermoplastic poly(urethane-co-carbonate) according to the invention has < 39 mol%, more preferably > 5 mol% to < 39 mol%, particularly preferably > 10 mol% to < 37 mol%, and most preferably > 15 mol% to < 36 mol% of aromatic groups, wherein this quantity refers to the total amount of aliphatic and aromatic groups. The aromatic content of a thermoplastic poly(urethane-co-carbonate) can be calculated via the stoichiometry of the starting materials. Preferably, the aromaticity is determined by 1H NMR spectroscopy. The person skilled in the art is able to determine the proportion of the polyurethane that consists of one or more 2024PF30150a

[0076] - 17 - aromatic diisocyanates, and to determine the proportion of polycarbonate using this method. For example, the polymer can be dissolved in CDCl₃. If an insoluble residue is obtained, dimethyl sulfoxide-d6 can also be used as a solvent. Tetramethylsilane is preferably used as a standard. It has been shown that a 600 MHz NMR spectrometer is generally sufficient to distinguish the individual proton signals of the polyurethane and / or polycarbonate. The aromaticity can be determined from the proportion of polyurethane by means of the molecular weight of the repeating unit of the polyurethane and the proportion of aromatic hydrocarbons contained therein. This is a method known to those skilled in the art and is preferred for determining the proportion of aromatic groups.

[0077] The thermoplastic poly(urethane-co-carbonate) has a proportion of > 1 mol% to < 99 mol%, preferably > 3 mol% to < 75 mol% carbonate groups, more preferably > 5 mol% to < 58 mol%, particularly preferably < 50 mol%, based on the sum of the carbonate and urethane groups in the poly(urethane-co-carbonate), wherein the mol% of carbonate and urethane groups are above 13The proportions of carbonate and urethane groups can be determined by 13C NMR spectroscopy. A person skilled in the art can determine the proportions of carbonate and urethane groups using this method. For example, the polymer can be dissolved in chlorform-dl (CDCL). If an insoluble residue is obtained, dimethyl sulfoxide-d6 (DMSO-d6) can also be used as a solvent. Tetramethylsilane is preferably used as a standard. It has been shown that a 600 MHz NMR spectrometer is generally sufficient to distinguish the individual carbon signals of the urethane and carbonate groups. The chemical shift of the signal of the carbon in the urethane group is typically in the range of 153.8 ppm (or 153.6 ppm when DMSO-d6 is used as the solvent). The carbon atom of the carbonate group is usually found at a chemical shift of 155.5 ppm (or 154.8 ppm when DMSO-d6 is used as the solvent) (see experimental section).To determine the mol% of carbon atoms, the area under the signals is integrated and compared to each other. This is a method known to those skilled in the art.

[0078] The poly(urethane-co-carbonate) according to the invention has a weight average of the molar mass (M w ) of at least 40,000 g / mol. Preferably, the poly(urethane-co-carbonate) according to the invention has a weight average molar mass of 40,000 g / mol to 300,000 g / mol, particularly preferably of 45,000 g / mol to 250,000 g / mol, and most preferably of 50,000 g / mol to 200,000 g / mol. It has been found that the inventive 2024PF30150a

[0079] - 18 -

[0080] Poly(urethane-co-carbonate) exhibits good properties in this defined molar mass range, particularly good thermoplasticity. Likewise, its mechanical properties, especially its tough and ductile behavior at least at room temperature, are good in this molar mass range.

[0081] This weight average of the molar mass (M) is preferred w) and / or all other molecular weights of the invention, unless otherwise specified, determined by gel permeation chromatography in degassed tetrahydrofuran (THF) as eluent with a polystyrene as standard (preferably in accordance with DIN EN ISO 13885-1:2021-11) using a polystyrene calibration. The GPC analysis unit comprises a pump (e.g., Agilent 1200 Infinity II IsoPump), an injector (e.g., Agilent 1100 Infinity II ALS), a column oven (e.g., Shimadzu CTO-10A), and preferably one or more commercially available GPC columns connected in series for size exclusion chromatography (e.g., PSS SDV 5pm, PSS SDV 1000Ä, PSS SDV 100Ä, PSS SDV 50Ä), selected to ensure sufficient separation of the molar masses of prepolymers and polymers. Detection is preferably performed via the refractive index (e.g., using an Agilent 1260 Infinity II RID). Calibration is performed using narrowly distributed polystyrene standards (e.g., for prepolymers).ReadyCal Kit Polystyrene low, Part Number: PSS-PSKITR1L, nominal Mp 266-66,000 Da, or for polymers, e.g., ReadyCal Kit Polystyrene, Part Number: PSS-PSKITR1, nominal Mp 474-2,520,000 Da). Molar mass mean values ​​outside this range are extrapolated. For sample preparation, 20-40 mg of sample are dissolved in 5-10 mL of THF with slow shaking for two hours and then filtered through a 0.45 pm PTFE filter. 40 pL of the solution are injected into the GPC analyzer and measured with degassed THF as the eluent at a flow rate of 0.6 mL / min and a temperature of 30 °C. The general method is defined at Currenta GmbH & Co. OHG under AM 2011-0623701 -09D, which can be requested from Currenta at any time.

[0082] It is preferred that the thermoplastic poly(urethane-co-carbonate) according to the invention comprises the structural formula (III) 2024PF30150a

[0083] - 19 - where each R 1the meanings mentioned in formula (I), whereby the group enclosed by the round brackets -CFF-R'-CIK- also partially has meanings independent of each other for R 6 can stand, provided that at least part of the structures is -CFF-R'-CFF-, and R 6 represents an aliphatic alkylene group with 4 to 20 carbon atoms, which may be linear or branched or may have at least one cycle, wherein the at least one cycle may have at least one heteroatom, where R 6 , if R 6 has at least one cycle, is not incorporated into the structure (III) via a CH2 group on at least one side, preferably on both sides, and each R 2The meanings mentioned in formula (II) are defined as follows: m is the arithmetic mean of the repeating units and is a number > 1.5, preferably > 2.0, further preferably > 2.5, even more preferably > 3.0, particularly preferably > 4.0, and most preferably > 5.0, and the wavy lines represent the connection of the structure of formula (III) to the poly(urethane-co-carbonate) chain. The arithmetic mean of the repeating units m is preferably a number < 25.0, particularly preferably < 21.0, and most preferably < 10.0.

[0084] A person skilled in the art can determine the arithmetic mean of repetition units m using known methods. Further details can be found later.

[0085] It is clear to those skilled in the art how the structure of formula (III) results from the structures of formulas (I), (II) and, if applicable, (1). Formula (III) is particularly preferably represented by the following formula (III). where each R 1 , R 2and m has the meanings mentioned for formula (III) and wherein the wavy lines in formula (11) represent the connection of the structure of formulas (11) to the poly(urethane-co-carbonate) chain. The person skilled in the art is aware that formula (11) can also be statistically interrupted by the presence of formulas (1). Most preferably, however, the polymer has no groups R 6 on.

[0086] Furthermore, it is preferred that the thermoplastic poly(urethane-co-carbonate) according to the invention, in addition to the structure of formula (III) or (III), contains 0 to 50 wt.%, preferably 0 to 30 wt.%. 2024PF30150a

[0087] - 20 -

[0088] wt.%, most preferably 0 to 15 wt.% repetition units of formula (IV) comprising where each R 1 the meanings mentioned in formula (I), whereby the group enclosed by the round brackets -CFF-R'-CFF- also partially represents R independently of each other.6 can stand, although preferably no R 6 is present, and R 6 The meanings mentioned for formula (li) are as follows: n is the arithmetic mean of the repeating units, and the wavy lines represent the linkage of the structure of formula (IV) into the poly(urethane-co-carbonate) chain. The arithmetic mean n is a statistically generated number. A person skilled in the art can determine the proportion of groups of formula (IV) using methods commonly available to them, such as NMR spectroscopy. The method may also depend on the type of monomers used.

[0089] The thermoplastic poly(urethane-co-carbonate) according to the invention particularly preferably has a structure of formula (Illii) where each R 1 the meanings mentioned in formula (I), whereby the group enclosed by the round brackets -CFL-R'-CFL- also partially has meanings independent of each other for R 6can stand, provided that at least part of the structures is -CFL-R'-CFL-, and R 6 the meanings mentioned in formula (li), and each R 2 the meanings mentioned in formula (II), where m and r are each the arithmetic mean of the respective repetition units, where m is a number > 1.5, preferably > 2.0, further preferably > 2.5, even more preferably > 3.0, particularly preferably > 4.0, most particularly preferably > 5.0, 2024PF30150a

[0090] - 21 - x or 1-x is the relative ratio of the respective repeating units to each other, and the wavy lines in formula (Illii) represent the connection of the structure of formulas (Illii) to the poly(urethane-co-carbonate) chain. Here, m is preferably a number < 25.0, particularly preferably < 21.0, and most preferably < 10.0.

[0091] It is preferred that r is at least 1. A person skilled in the art can correlate r with the molecular weight. It is evident that if r is 1, formula (Illii) is a repeating unit of the poly(urethane-co-carbonate) according to the invention. This unit can be statistically distributed within the poly(urethane-co-carbonate) according to the invention. It can also be bound to another repeating unit of formula (Illii). This results in r being greater than 1.

[0092] It is obvious to a person skilled in the art that x must be less than 1. If unreacted diol, in particular of formula (1a) and possibly of formula (X), is present, then x is less than 1.

[0093] It is evident to those skilled in the art that the end groups in formula (Illii) do not necessarily have to be methyl groups, but merely represent a potential end of the chain of formula (Illii) or can be a further point of attachment to other groups. Most preferably, the thermoplastic poly(urethane-co-carbonate) according to the invention has a structure of formula (Illii), but without R 6 is available.

[0094] The thermoplastic poly(urethane-co-carbonate) preferably has a glass transition temperature above > 70°C, more preferably > 70°C to < 160°C, particularly preferably > 80°C to < 155°C, and most preferably > 90°C to < 150°C. The glass transition temperature (Tg) can be... g The temperature is preferably determined by differential scanning calorimetry (DSC) according to DIN EN ISO 11357-1:2022-02 and DIN EN ISO 11357-2:2020-08. In particular, a heating rate of 20 K / min under nitrogen is used, and the temperature is determined as follows: gThe inflection point in the second heating process is determined. A glass transition temperature within the defined range enables the thermoplastic poly(urethane-co-carbonate) according to the invention to be used in common plasticizing processes (e.g., injection molding, (co)extrusion, blow molding, thermoforming).

[0095] The thermoplastic poly(urethane-co-carbonate) according to the invention, which is preferably obtained by the process according to the invention, can be processed as such into molded bodies of all kinds. It can also be processed with other thermoplastics and / or polymer additives to form thermoplastic molding compounds, which are then formed into molded bodies. 2024PF30150a

[0096] - 22 - are further objects of the present invention. The molded bodies and the molding compounds made of a thermoplastic composition containing the thermoplastic poly(urethane-co-carbonate) according to the invention are further objects of the present invention. The polymer additives are preferably selected from the group consisting of flame retardants, anti-dripping agents, flame retardant synergists, smoke inhibitors, lubricants and demolding agents, nucleating agents, antistatic agents, conductivity additives, stabilizers (e.g., thermostabilizers, hydrolysis and heat aging stabilizers, and transesterification inhibitors), flow promoters, phase compatibility mediators, dyes and pigments, impact modifiers, and fillers and reinforcing agents.

[0097] The molded parts, made from a thermoplastic composition containing the inventive thermoplastic poly(urethane-co-carbonate), can be produced, for example, by injection molding, extrusion, and blow molding. Another processing method is the production of molded parts by deep drawing from previously manufactured sheets or films.

[0098] In a further aspect of the present invention, a process for producing a poly(urethane-co-carbonate), preferably a thermoplastic poly(urethane-co-carbonate), as described above, is provided, comprising the process steps

[0099] (i) Implementation of at least one aliphatic diol of formula (1a)

[0100] HO — CH2 — R 1 - CH2— OH ZT ,

[0101] (1a), where each R 1in formula (1a) each independently represents an aliphatic group with 4 to 18 carbon atoms, which has at least one cycle and this cycle may optionally contain at least one heteroatom, with at least one aromatic diisocyanate of formula (1a) where R 2 in the formula (Ila) stands for a bridging aromatic structure with 6 to 18 carbon atoms, to a prepolymer and 2024PF30150a

[0102] - 23 -

[0103] (ii) Reaction of the prepolymer obtained from process step (i) with a diaryl carbonate in the presence of at least one catalyst to obtain the poly(urethane-co-carbonate), characterized in that in process step (i) the molar ratio of all diols used to all diisocyanates used is 5.0:1.0 to 1.01:1.0 and that, apart from the diisocyanates of formula (Ila), no non-aromatic diisocyanates are used. Thus, only aromatic diisocyanates are used.

[0104] The person skilled in the art is able to see the connection between the inventive process and the inventive thermoplastic poly(urethane-co-carbonate). In particular, he can see the connection between formulas (1a) and (1a) and formulas (I), (II), (III), (III), (IIII), (IIIII) and (IV).

[0105] The method according to the invention is preferably characterized in that the thermoplastic poly(urethane-co-carbonate) according to the invention is produced in all embodiments, preferences, and combinations thereof. In a further aspect of the present invention, a thermoplastic poly(urethane-co-carbonate) is provided which is obtained by the method according to the invention in all embodiments, preferences, and combinations thereof. This is preferably the thermoplastic poly(urethane-co-carbonate) according to the invention.

[0106] The molar ratio of all diols used, but especially of the (cyclo)aliphatic diol of formula (1a), to all diisocyanates used, which according to the invention are all aromatic, can be used to influence, among other things, the resulting proportion of carbonate groups and urethane groups in the poly(urethane-co-carbonate).

[0107] The molar ratio of all diols used to all diisocyanates used in the process according to the invention (step (i)) is 5.0: 1.0 to 1.01: 1.0, preferably 3.5: 1.0 to 1.05: 1.0, more preferably 3.0: 1.0 to 1.1: 1.0.

[0108] In process step (i), at least one aliphatic diol of formula (1a) is used. It is evident that only one aliphatic diol of formula (1a) can be used as the diol. This can be one or more aliphatic diols of formula (1a). In particular, it is evident that if R 1 If it has more than one cycle, one or more of the 4 to 18 carbon atoms can also be part of two cycles. R 1 In the formula (aa), each independently represents an aliphatic group with 4 to 2024PF30150a.

[0109] - 24 -

[0110] 18 carbon atoms, which has at least one cycle and wherein this cycle may optionally contain at least one heteroatom, preferably oxygen.

[0111] The inventive method is particularly preferred in that R 1 represented in formula (1a) by formula (1) or formula (2), where the positions marked with the stem “*” in formulas (1) and (2) are the positions where the CFF groups shown in formula (1a) are located.

[0112] In addition to the aliphatic diol of formula (1a), one or more further diols may also be used in process step (i). It is preferred that the one or more further diols are used in process step (i) in a proportion of at most 75 mol%, more preferably at most 60 mol%, even more preferably at most 40 mol%, even more preferably at most 25 mol%, particularly preferably at most 10 mol%, and most preferably at most 5 mol%, relative to all diols used. Preferably, no further diol is used in addition to the at least one aliphatic diol of formula (1a).

[0113] The one or more additional diol(s) in process step (i) preferably comprises at least one diol of formula (X)

[0114] HO-R 6 -OH (X), where each R 6for an aliphatic alkylene group having 4 to 20, preferably 5 to 18, particularly preferably 6 to 16 carbon atoms, which may be linear or branched or may have at least one cycle, wherein the at least one cycle may have at least one heteroatom, and wherein, if R 6 has at least one cycle, at least one OH group does not belong to a primary alcohol group. "That at least one OH group does not belong to a primary alcohol group" means that at least one of the OH groups is not incorporated into formula (X) via a CH2 group, but rather is a secondary or tertiary alcohol function. Preferably, both OH groups are not incorporated into formula (X) via a CH2 group. It is understood that "incorporated via..." means that the corresponding incorporating 2024PF30150a

[0115] - 25 -

[0116] The group is part of formula (X). In this context, it is understood that, according to the invention, reference is often made to "at least" one compound such as a diol or a diisocyanate and to "another" compound. The compound designated as "at least" is mandatory, and the other compound(s) may be present in addition. Accordingly, the person skilled in the art can also determine the ratios of the diols to the diisocyanates.

[0117] In process step (i), at least one aromatic diisocyanate of formula (Ila) with 6 to 18 carbon atoms is used. It is evident that this aromatic diisocyanate of formula (Ila) can be used as the sole diisocyanate. It is understood that one or more aromatic diisocyanates of formula (Ila) can also be used, but preferably no other aromatic diisocyanate is used besides those of formula (Ila). R 2In formula (Ila) the above-mentioned meanings of R are preferred. 2 to formula (II). In particular, R 2 for a bridging aromatic structure with 6 to 18 carbon atoms. The process according to the invention is particularly preferably characterized in that the structure R 2 in formula (Ila) is represented by one of the formulas (3) to (6), where each R 3 in formula (3) independently represents a methyl or ethyl group, p represents 0, 1, or 2, and q represents 0 or 1, and each R 3 In formula (4), p represents a methyl or ethyl group independently of each other, and p represents 0, 1, or 2, and d represents 0 or 1 independently of each other. Preferably, in addition to the at least one aromatic diisocyanate of formula (Ila), no further 2024PF30150a is used.

[0118] - 26 -

[0119] Diisocyanate is used. It goes without saying that mixtures of these compounds can also be used.

[0120] In addition to the aromatic diisocyanate of formula (Ila), one or more further aromatic diisocyanates may also be used in process step (i). It is preferred that at most 75 mol%, more preferably at most 60 mol%, even more preferably at most 40 mol%, even more preferably at most 25 mol%, particularly preferably at most 10 mol%, and most preferably 5 mol%, based on the at least one diisocyanate of formula (Ila), are used. "Up to" here means that the respective limit mentioned is included within the described range. However, it is most preferably that no further diisocyanate is used in addition to the at least one aromatic diisocyanate of formula (Ila).

[0121] Particularly preferred in process step (i) of the inventive process is at least one aliphatic diol of formula (1a), wherein R 1 the formula (1) and / or (2) is used and at least one aromatic diisocyanate of formula (Ila), in which R 2 is represented by a structure of formula (3), where p = 0 and q = 1, and / or (4), where R 3 a methyl group, p = 1 and d = 0. The structure of formula (3) with p = 0 and q = 1 is particularly preferably a mixture of different structures. A mixture of 4,4'- and 2,4'- and optionally 2,2'-isomers is preferred. Furthermore, a mixture in which at least 80 mol% of the structures are 4,4'-isomers and the remainder are 2,4'- or 2,2'-isomers is preferred. The structure of formula (4) with R is particularly preferably 3The methyl group, p = 1 and d = 0, is a mixture of different structures. A mixture is preferred in which at least 80 mol% of the structures are the 2,4-isomer and the remainder are the 2,2-isomer. The 2,4-isomer with structure (4) is particularly preferred as the diisocyanate. Most preferably, no other diol or diisocyanate is used in addition to these diols and diisocyanates.

[0122] In process step (i), at least one diol of formula (1a) can be introduced. In this case, at least one diisocyanate of formula (1a) is subsequently added, either completely or over a longer period. However, it is also possible for at least one diol of formula (1a) and at least one diisocyanate (1a) to be fed into the reactor at the same time. Process step (i) is preferably carried out in a heating medium temperature range of 100 °C to 265 °C, more preferably from 110 °C to 260 °C, and particularly preferably from 120 °C to 255 °C.

[0123] - 27 - particularly preferably carried out from 130 °C to 250 °C. The reaction is exothermic, so the reaction can preferably also be carried out by cooling.

[0124] Process step (i) can be carried out under nitrogen at normal pressure. However, the process step can also be carried out under reduced or increased pressure.

[0125] Process step (i) is preferably carried out until all diisocyanates present have essentially reacted. This can be verified, for example, by determining the NCO content.

[0126] The viscosity of the mixture generally increases during process step (i). It is advantageous to carry out thorough mixing in process step (i). In some cases, it may also be advantageous to perform process step (i) in the presence of a solvent. This is particularly the case when a highly viscous prepolymer is obtained. Aromatic hydrocarbons, especially chlorobenzene, are preferably used for this purpose. It is preferred that no solvent is present in process step (i). This eliminates the need for an additional solvent removal step.

[0127] According to the invention, a polymer with a high glass transition temperature of at least 70 °C is obtained by using a cycloaliphatic diol and an aromatic diisocyanate. Furthermore, it has proven particularly advantageous to at least partially remove the (unreacted) aliphatic diol (of formula (1a) and optionally formula (X)) that remains after process step (i). This allows the glass transition temperature to be influenced and further increased. This enables a targeted adjustment of the glass transition temperature, which also always depends on the chemical nature of the diols and diisocyanates used. It is evident to those skilled in the art how the presence or absence of the repeating unit (IV) shown above can thus be influenced, among other things.For example, the thermoplastic poly(urethane-co-carbonate) according to the invention typically contains repeat units of formula (IV) if, at the beginning of process step (ii), previously unreacted diols are still present in the prepolymer.

[0128] Process step (i) can be carried out in the absence or presence of at least one catalyst. Preferably, process step (i) is carried out in the absence of a catalyst. If a catalyst is used in process step (i), urethanization catalysts known to those skilled in the art may be used. Particularly preferably, aliphatic catalysts 2024PF30150a

[0129] - 28 - tertiary amines (for example, bis(dimethylaminoethyl) ether, pentamethyldiethylenetriamine), cycloaliphatic tertiary amines (for example, 1,4-diaza(2,2,2)bicyclooctane), aliphatic amino ethers (for example, dimethylaminoethyl ether and N,N,N-trimethyl-N-hydroxyethyl bisaminoethyl ether), cycloaliphatic amino ethers (for example, N-ethylmorpholine), aliphatic amidines, cycloaliphatic amidines, urea, derivatives of urea (such as aminoalkyl hams), in particular (3-dimethylaminopropylamine) hams), and tin catalysts (such as monoalkyltin oxide, dialkyltin oxide, dialkyltin dilaurate, tin octoate) are used.

[0130] Preferably, (A) urea, urea derivatives, and / or (B) the amines and amino ethers mentioned above can be used as catalysts, characterized in that the amines and amino ethers contain a functional group that reacts chemically with the isocyanate. Preferably, the functional group is a hydroxyl group, a primary, or a secondary amino group. These particularly preferred catalysts have the advantage of exhibiting significantly reduced migration and emission behavior. Examples of particularly preferred catalysts include: (3-Dimethylaminopropylamine)-Hame, 1,1'-((3-(dimethylamino)propyl)imino)bis-2-propanol, N-[2-[2-

[0131] (dimethylamino)ethoxy]ethyl]-N-methyl-1,3-propanediamine and 3-

[0132] Dimethylaminopropylamine and its derivatives and comparable molecules in which the dimethylamino group is replaced by a pyrrolidine group according to WO 2022 / 112157 Al.

[0133] The use of monobutyltin oxide and / or dibutyltin oxide as a catalyst in process step (i) is particularly preferred.

[0134] If a catalyst is used in process step (i), it is preferably used in an amount of 1 ppm to 1000 ppm, particularly preferably 30 to 500 ppm, most preferably 50 to 170 ppm, based on the mass of all diisocyanates used.

[0135] Within the scope of the present invention, ppb and ppm are to be understood as weight-related values ​​unless otherwise specified.

[0136] The prepolymer obtained by process step (i) is (essentially) OH-terminated by the defined ratio of diol to diisocyanate. Furthermore, unreacted aliphatic diol of formula (1a) (or formula (X), if present) is usually still present immediately after completion of process step (i), since an excess of diol 2024PF30150a

[0137] - 29 - was used. This diol(s) may be present in process step (ii) or removed beforehand.

[0138] In one aspect of the inventive process, it is characterized in that at least a portion of the unreacted aliphatic diol of formula (1a) is removed from the prepolymer between process steps (i) and (ii). If present, at least one further aliphatic diol, preferably of formula (X), can also be removed.

[0139] Preferably, the unreacted aliphatic diol of formula (1a) (and optionally of formula (X)) is removed, for example, by distillation, precipitation, and / or thin-film evaporation. Those skilled in the art are familiar with various methods that can be used to remove the aliphatic diol of formula (1a).

[0140] In process step (ii), the prepolymer obtained from process step (i) is reacted with a diaryl carbonate in the presence of at least one catalyst. According to the invention, the diaryl carbonate is also occasionally referred to as the carbonyl source. Depending on whether at least partially unreacted diol of formula (1a) and possibly formula (X) is still present in the prepolymer, it can also react with the diaryl carbonate in process step (ii).

[0141] Preferably, the diaryl carbonate is used in a molar ratio of 1.2:1 to 0.95:1, particularly preferably 1.11:1 to 0.98:1, and most preferably 1.07:1 to 0.99:1 with respect to the OH groups present (the first number represents the diaryl carbonate and the second number represents the OH groups present). These can originate from the prepolymer of process step (i) and optionally also from unreacted diol and / or further diol. The OH groups of the prepolymer are preferably determined by calculating the OH number, as described later. However, they can also be calculated theoretically.

[0142] According to the invention, it may be possible that process steps (i) and (ii) cannot be completely separated. For example, the diaryl carbonate from process step (ii) and the catalyst used in process step (ii) may already be present in process step (i). In this case, it is not entirely possible to prevent the intended reaction of process step (ii) from occurring to a small extent in process step (i). However, this can be minimized (e.g., by controlling the temperature). According to the invention, it is intended that a reaction of OH groups with NCO groups takes place first (process step (i)) and only then does reaction 2024PF30150a occur.

[0143] - 30 - of OH groups with the diaryl carbonate occurs (process step (ii)). The person skilled in the art is able to carry out these intended reactions in such a way that they take place mainly in the aforementioned order.

[0144] Preferably, the prepolymer obtained from process step (i) is not isolated. This means that process step (ii) preferably follows process step (i) immediately. As described above, this can be achieved, for example, by increasing the temperature and applying a vacuum if the diaryl carbonate and the catalyst are already at least partially present in process step (i). Alternatively, this can be achieved by adding the diaryl carbonate and / or the catalyst, increasing the temperature, and applying a vacuum.

[0145] Process step (ii) is preferably carried out at a heating medium temperature of 200°C to 270°C, particularly preferably 210°C to 265°C, and most preferably at 220°C to 260°C. The specified temperature is preferably the final temperature. According to the invention, it is possible to reach the final temperature by gradually increasing the temperature.

[0146] In the reaction of process step (ii), a condensation product is generally formed. To shift the equilibrium of the reaction, it is advantageous to apply a vacuum during process step (ii). The vacuum in process step (ii) is preferably 500 mbar to 0.01 mbar, more preferably 200 mbar to 0.01 mbar. In particular, it is preferred that the vacuum be reduced stepwise. Most preferably, the vacuum in the last stage is 10 mbar to 0.01 mbar.

[0147] The process according to the invention is preferably characterized in that the at least one catalyst present in process step (ii) is an ammonium salt, a phosphonium salt, or an organic base. A person skilled in the art is able to select the appropriate catalyst depending on the reactivity of the substances used.

[0148] All inorganic or organic basic compounds can be used as catalysts for process step (ii), for example lithium, sodium, potassium, cesium, magnesium, calcium, barium, yttrium, titanium, manganese, iron, zinc, tin, bismuth, hydroxides, carbonates, halides, phenolates, diphenolates, alcoholates, enolates, fluorides, acetates, phosphates, hydrogen phosphates, boranates, oxides, nitrogen and phosphorus bases such as tetramethylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium fluoride, tetramethylammonium tetraphenylboranate, 2024PF30150a

[0149] - 31 -

[0150] Tetraphenylphosphonium fluoride, tetraphenylphosphonium tetraphenylboranate,

[0151] Dimethyldiphenylammonium hydroxide, tetraethylammonium hydroxide,

[0152] Cethyltrimethylammonium tetraphenylboranate, cethyltrimethylammonium phenolate, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or guanidine systems such as l,5,7-triazabicyclo[4,4.0]-dec-5-ene (TBD), 7- Phenyl-l,5,7-triazabicyclo-[4,4,0]-dec-5-ene, 7-methyl-l,5,7-triazabicyclo-[4,4,0]-dec-5-ene, 7,7'-hexylidenedi-l,5,7-triazabi-cyclo-[4,4,0]-dec-5-ene, 7,7'-Decylidenedi-l,5,7-triazabicyclo- [4,4,0]-dec-5-ene, 7,7'-dodecylidene-di-1,5,7-tri-aza-bicyclo-[4,4,0]-dec-5-ene or phosphazenes such as the phosphazene base Pl-t-Oct = tert. -Octyl -imino-tris- (dimethylamino)-phosphorane, phosphazene base Pl-t-butyl = tert. -Butyl-imino-tris-(dimethylamino)-phosphorane, BEMP = 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diaza-2-phos-phoran, in question.

[0153] Phosphonium catalysts of formula (VIII) are particularly suitable:

[0154] X (VIII) wherein Ra, Rb, Rc and Rd may be the same or different Ci to Cio alkyls, Ce to Ci 4-aryles, C7 to Cis arylalkyls or C5 to Ce cycloalkyls, preferably methyl or Ce to C14-aryles, particularly preferably methyl or phenyl, and X may be an anion such as hydroxide, sulfate, hydrogen sulfate, hydrogen carbonate, carbonate or a halide, preferably chloride or an alkylate or arylate of the formula -OR, wherein R may be a Ce to Ci4-aryl, C7 to C15-arylalkyl or C5 to Ce cycloalkyl, preferably phenyl.

[0155] Particularly preferred catalysts are monobutyltin oxide, dibutyltin oxide, lithium hydroxide, lithium acetate dihydrate, sodium acetate trihydrate, sodium 2-ethylhexanoate, magnesium acetate tetrahydrate, manganese acetate tetrahydrate, zinc acetate, iron(II) acetate, cesium carbonate, tetraisopropyl orthotitanate, titanium 2-ethylhexanoate, bismuth tris(2-ethylhexanoate), and yttrium 2-ethylhexanoate. Monobutyltin oxide, dibutyltin oxide, sodium 2-ethylhexanoate, zinc acetate, and tetraisopropyl orthotitanate are especially preferred. Sodium methylate is also preferred.

[0156] These catalysts can be in the quantity range of 0.1 to 1000 ppm, preferably in the range of 0.5 to 500 ppm and particularly preferably in the range of 1 to 200 ppm, entirely 2024PF30150a

[0157] - 32 - particularly preferably in the range of 1 to 100 ppm with respect to the total starting materials (diol(s) + diisocyanate(s) + diaryl carbonate).

[0158] In process step (i) according to the invention, a prepolymer is produced. The prepolymer, preferably produced by process step (i), is also the subject of the present invention.

[0159] According to the invention, a prepolymer is understood to be the precursor of a polymer. The urethanediol prepolymer is composed of the building blocks diol and diisocyanate. It is a reactive oligomer. In the prepolymer according to the invention, terminal OH groups are reactive functionalities.

[0160] The OH-terminated prepolymer preferably comprises the structural formula (V) where each R 1in formula (V) each independently represents an aliphatic group with 4 to 18 carbon atoms, which has at least one cycle and where this cycle may optionally contain at least one heteroatom, and where the group enclosed by the round brackets -CH2-R'-CH2- also partially represents R each independently 6 can be, provided that at least part of the structures is -CH2-R'-CH2-, and R 6 for an aliphatic alkylene group with 4 to 20 carbon atoms, which may be linear or branched or may have at least one cycle, wherein the at least one cycle may have at least one heteroatom, and wherein R 6 , if R 6 has at least one cycle, is not incorporated into the structure (V) via a -CH2 group on at least one side, and where each R 2In formula (V), each independently represents a bridging aromatic structure with 6 to 18 carbon atoms, and where m is the arithmetic mean of the repeating units and is a number > 1.5, preferably > 2.0, further preferably > 2.5, even more preferably > 3.0, particularly preferably > 4.0, and most preferably > 5.0. Here, m is preferably a number < 25.0, particularly preferably < 21.0, and most preferably < 10.0. 2024PF30150a

[0161] - 33 -

[0162] This prepolymer is further preferably an OH-terminated urethane prepolymer with a build-up factor as defined below, having a structure of formula (Va) where each R 1 in formula (Va) each independently represents an aliphatic group with 4 to 18 carbon atoms, which has at least one cycle and wherein this cycle may optionally contain at least one heteroatom and wherein each R 2In formula (Va), each instance independently represents a bridging aromatic structure with 6 to 18 carbon atoms, and where m is the arithmetic mean of the repeating units and is a number > 1.5, preferably > 2.0, further preferably > 2.5, even more preferably > 3.0, particularly preferably > 4.0, and most preferably > 5.0. Here, m is preferably a number < 25.0, particularly preferably < 21.0, and most preferably < 10.0.

[0163] Preferably, only diols of formula (1a) and diisocyanates of formula (1a) are used, so that the prepolymer only comprises corresponding structural units.

[0164] A urethane prepolymer contains the urethane group -NH-CO-O-. The build-up factor, denoted as "m" in formula (V), indicates how many diisocyanate units the prepolymer comprises. It is the arithmetic mean of the repeating units found in square brackets. The build-up factor is limited by the fact that it is a "prepolymer," i.e., a reactive building block, containing terminal OH groups as reactive functionalities.

[0165] A person skilled in the art can determine the arithmetic mean of repeating units m by known methods. In particular, m can be determined by gel permeation chromatography; preferably, the gel permeation chromatography method described in the example section is used. This yields different peaks which can be assigned to corresponding oligomers based on their molecular weight. If the peaks are not clearly separated (especially in the case of 2024PF30150a),

[0166] - 34 - longer-chain oligomers) the peak subdivision can preferably be placed at the minimum point between two peaks. If no minimum point is measured, the tailing of the peak is preferably still counted towards the corresponding repetition unit of the maximum (see also the example section and Figures 2 and 4). The weighted arithmetic mean of the repetition unit m can be calculated from the areas.

[0167] A particularly preferred OH-terminated urethane prepolymer according to the invention is one in which R 1 is represented by where the positions marked with the stem in formulas (1) and (2) are the positions where the CFF groups shown in formula (V) and (Va) are located respectively, and R 2 represented by one of the formulas (3) or (4), where each R 3 in formula (3) independently represents a methyl or ethyl group, p represents 0, 1, or 2 and q represents 0 or 1, where p = 0 and q = 1 is particularly preferred, and each R 3 in formula (4) independently represents a methyl or ethyl group, and p represents 0, 1, or 2, and d represents 0 or 1 independently, wherein R is particularly preferably 3for a methyl group, p = 1 and d = 0, and where the positions marked with the stem in formulas (3) and (4) are the positions where the nitrogen atoms shown in formula (V) and formula (Va) are located respectively.

[0168] It is understood that the corresponding diols and / or diisocyanates can also be used in mixtures, so that corresponding mixtures are present in the prepolymer 2024PF30150a

[0169] - 35 - and R 1 in the prepolymer, for example, is represented partly by formula (1) and partly by formula (2) and / or R 2 in the prepolymer is thus partly represented by formula (3) and partly by formula (4). “In the R 1 "is represented by" therefore does not exclude the possibility that R 1 can also result from mixtures of diols, provided the definition of R 1 is satisfied. The same applies to R. 2However, according to the invention, it is preferred that only a single diol and a single aromatic diisocyanate are used for the production of the thermoplastic poly(urethane-co-carbonate) and thus also for the production of the urethanediol prepolymer. It is understood that these can also be isomer mixtures.

[0170] "OH-terminated" means that OH groups are present at both ends of the urethane prepolymer chain. The prepolymer can therefore also be referred to as "urethanediol prepolymer" or "urethanediol." A person skilled in the art can determine the amount of reactive OH groups using known methods. In particular, the number of OH groups can be determined by titration as the hydroxyl number (also called the OH number) in mg KOH / g. The OH number of the urethane prepolymers is preferably between 14 and 700 mg KOH / g, more preferably between 16 and 600 mg KOH / g, particularly preferably between 18 and 500 mg KOH / g, and most preferably between 20 and 400 mg KOH / g, wherein the OH number is preferably determined by titration in accordance with DIN EN ISO 4629-2, where "in accordance with" means that pyridine is used instead of the base A'-mcthyl-2-pyrrolidone. This method is defined by Currenta GmbH & Co. OHG as method no. 2011-0232602-92D, which can be requested from them.

[0171] Preferably, the prepolymer has a number-average molecular weight M n in the range of 200 g / mol to 10,500 g / mol, more preferably 300 g / mol to 9,500 g / mol, particularly preferably 400 to 8,500 g / mol, and most preferably 500 to 7,500 g / mol. This number-averaged molecular weight M is preferred. n determined by gel permeation chromatography. This weight average of the molar mass (M) is particularly preferred. n) and / or all other molecular weights of the invention, unless otherwise specified, are determined by gel permeation chromatography in degassed tetrahydrofuran (THF) as the eluent using polystyrene as a standard (preferably in accordance with DIN EN ISO 13885-1:2021-11) using a polystyrene calibration. The GPC analysis unit comprises a pump (e.g., Agilent 1200 Infinity II IsoPump), an injector (e.g., Agilent 1100 Infinity II ALS), a column oven (e.g., Shimadzu CTO-10A), and preferably one or more commercially available GPC columns connected in series for size exclusion chromatography (e.g., PSS SDV 5pm, PSS SDV 1000Ä, PSS SDV 100Ä, PSS SDV 50Ä), 2024PF30150a

[0172] - 36 - which are selected to allow sufficient separation of the molar masses of prepolymers and polymers. Detection is preferably performed via the refractive index (e.g., using an Agilent 1260 Infinity II RID). Calibration is performed using narrowly distributed polystyrene standards (for prepolymers, e.g., ReadyCal Kit Polystyrene low, Part Number: PSS-PSKITR1L, nominal Mp 266–66,000 Da, or for polymers, e.g., ReadyCal Kit Polystyrene, Part Number: PSS-PSKITR1, nominal Mp 474–2,520,000 Da). Molar mass mean values ​​outside this range are extrapolated. For sample preparation, 20–40 mg of sample are dissolved in 5–10 mL of THF with slow shaking for two hours and then filtered through a 0.45 pm PTFE filter. 40 pL of the solution are injected into the GPC analyzer and measured with degassed THF as eluent at a flow rate of 0.6 mL / min and a temperature of 30 °C. The general method is available from Currenta GmbH & Co.OHG defined under AM 2011-0623701 -09D, which can be requested from Currenta at any time.

[0173] The prepolymer according to the invention preferably has a glass transition temperature T g from > 0°C to < 145°C, more preferably from > 0°C to < 140°C, even more preferably from > 0°C to < 135°C, particularly preferably from > 0°C to < 130°C, wherein the glass transition temperature is determined by means of differential calorimetry, preferably in accordance with the standards DIN EN ISO 11357-1:2022-02 and DIN EN ISO 11357-2:2020-08 at a heating rate of 20 K / min.

[0174] Figures:

[0175] Figure 1: GPC spectrum of a prepolymer (example 5) based on CHDM and MDI in the molar ratio used of 3:1 (diocdiisocyanate) plotted against the molar mass.

[0176] Figure 2: Illustration of the subdivision of the GPC spectrum of a prepolymer (example 5) for determining the arithmetic mean of the repeating unit “m” of the prepolymer and, if applicable, the residual diol content; the designations A to G stand for individual peaks that must therefore be considered separately.

[0177] Figure 3: GPC spectrum of a prepolymer (Example 2) based on CHDM and MDI in the molar ratio used of 1.25:1 (dioxine diisocyanate) plotted against the molar mass. 2024PF30150a

[0178] - 37 -

[0179] Figure 4: Illustration of the subdivision of the GPC spectrum of a prepolymer (Example 2) for determining the arithmetic mean of the repeating unit “m” of the prepolymer and, if applicable, the residual diol content; the designations A to M stand for individual peaks that must therefore be considered separately.

[0180] Figure 5: 13C-NMR spectrum of a poly(urethane-co-carbonate) (Example 9) based on CHDM and MDI in the molar ratio used of 1.25:1 (DiocDiisocyanate).

[0181] Figure 6: 'H-NMR spectrum of a poly(urethane-co-carbonate) (Example 9) based on CHDM and MDI in the molar ratio used of 1.25:1 (DiocDiisocyanate).

[0182] Examples

[0183] Materials used:

[0184] Diol component (according to formula (1a))

[0185] CHDM (1) 1,4-Cyclohexanedimethanol: Mixture of cA-1,4-Cyclohexanedimethanol and trara- 1,4-Cyclohexanedimethanol, CAS: 105-08-8, 99%, Sigma Aldrich, Germany, was used without further purification

[0186] TCD-DM (2) Tricyclodecandimethanol: mixture of isomers, CAS: 26896-48-0, 96%, Sigma-Aldrich, Germany, was used without further purification

[0187] Diisocyanate component (according to formula (Ila))

[0188] MDI diphenylmethane-4,4'-diisocyanate, CAS: 101-68-8, Covestro AG,

[0189] Germany, was stored at 45 °C and used without further cleaning.

[0190] TDI Toluene-2,4-diisocyanate, CAS: 584-84-9, Covestro AG, Germany, was used without further purification.

[0191] Carbonyl source (for using the urethanediol prepolymer for PUC production)

[0192] DPC Diphenylcarbonate, CAS: 102-09-0, Covestro AG, Germany, was freshly distilled before use.

[0193] Catalyst (for the use of the urethanediol prepolymer for PUC production)

[0194] Katl monobutyltin oxide, CAS: 2273-43-0, TIB Chemicals AG, Germany, was used without further purification 2024PF30150a

[0195] - 38 -

[0196] Kat2 solution (5 g / L) of sodium 2-ethylhexanoate, CAS: 19766-89-3, Sigma

[0197] Aldrich, Germany, was used without further purification, in methyl tert-butyl ether (MTBE, CAS: 1634-04-4, > 99 wt.%), Sigma Aldrich, Germany, was used without further purification.

[0198] Kat3 solution (100 g / L) of tetrabutylphosphonium acetate, CAS: 17786-43-5, in methyl ethyl ketone (MEK, CAS: 78-93-3, > 99 wt.%, Sigma Aldrich, Germany, was used without further purification)

[0199] Analytical methods:

[0200] GPC:

[0201] The molar mass distribution was determined by Currenta GmbH & Co. OHG using gel permeation chromatography (GPC). Approximately 30 mg of the sample was weighed and dissolved in THF for 2 h with slow shaking. The sample was then filtered through a 0.45 pm PTFE filter and analyzed using a suitable GPC system with SDV columns (e.g., PSS SDV 5 pm, PSS SDV 1000 μ, PSS SDV 100 μ, PSS SDV 50 μ). Calibration was performed using narrowly distributed polystyrene standards (e.g., ReadyCal Kit Polystyrene low, Part Number: PSS-PSKITR1L, nominal Mp 266–66,000 Da for prepolymers, or ReadyCal Kit Polystyrene, Part Number: PSS-PSKITR1, nominal Mp 474–2,520,000 Da for polymers) and adjusted to the specific columns and samples. Degassed THF was used as the eluent. Detection was performed using a refractive index detector (RI). The general method is available from Currenta GmbH & Co.OHG defined under AM 2011-0623701-09D, which can be requested from Currenta at any time.

[0202] Determination of the arithmetic mean of the repeating unit m in urethanediol prepolymers

[0203] In the prepolymer synthesis, the diol component was always used in excess of the diisocyanate component. This led to the formation of oligomers with an arithmetic mean of the repeating unit m (compare, for example, formula (Va)), which resulted in a certain proportion of the diol component remaining unreacted in the mixture (as can be seen in the GPC spectrum of example 5 in Figure 1).

[0204] The determination of this arithmetic mean of the repetition unit m and the residual diol quantity is explained below approximately using Example 5. 2024PF30150a

[0205] - 39 -

[0206] The weight percentages of both the prepolymer and the remaining unreacted diol were determined from the GPC spectra plotted against the elution volume (Figure 1). Each detected peak, if clearly identifiable, was assigned to either the unreacted monomer diol or the oligomers based on its molecular weight. If the peaks were not clearly separated, which was often the case with longer-chain oligomers, the division was preferably performed at the nadir between two peaks until no nadir was measured (as shown in the GPC spectrum of Example 5 in Figure 2).

[0207] The following areas F (in %) were obtained from the GPC spectrum in Figure 2 for example 5:

[0208] A: Prepolymer with repeating unit m = 6 (F = 2.3%) (here it is evident that oligomers with a higher repeating unit are also included, the value is nevertheless artificially designated as "6")

[0209] B: Prepolymer with repeating unit m = 5 (F = 2.6%)

[0210] C: Prepolymer with repeating unit m = 4 (F = 5.3%)

[0211] D: Prepolymer with repeating unit m = 3 (F = 11.0%)

[0212] E: Prepolymer with repeating unit m = 2 (F = 22.5%)

[0213] F: Prepolymer with repeating unit m = 1 (F = 37.6%)

[0214] G: Residual diol CHDM (F = 18.7%)

[0215] m was determined according to the weighted arithmetic mean.

[0216] 1 x F(m = 1) + 2 x F(m = 2) + — I- nx F(m = ri) m = -

[0217] F Prepolymer)

[0218] With F(Prepolymer) = 81.3%

[0219] 1 x 37.7 + 2 x 22.5 + 3 x 11.0 + 4 x 5.4 + 5 x 2.6 + 6 x 2.3 m = - — — - = 2.0

[0220] 81.3

[0221] The arithmetic mean of the repetition unit "m" for example 5 is 2.0.

[0222] It is also clear to those skilled in the art that with a smaller excess of the diol component, the determination of m via GPC is less accurate, since the higher oligomers (m > 5) merge into each other in the GPC spectrum due to the low resolution.

[0223] In these cases, a unique assignment of the oligomers using GPC is not possible, so the arithmetic mean of the repeating unit m can only be approximated as 2024PF30150a

[0224] - 40 - can be determined as a minimum size (represented by a ">"), as shown in Example 2 and described below (see Figures 3 and 4).

[0225] The following areas F (in %) were obtained from the GPC spectrum in Figure 4 for Example 2:

[0226] A: Prepolymer with repeating unit m = 9 (F = 37.6%) (here it is evident that oligomers with a higher repeating unit are also included, the value is nevertheless artificially referred to as "9")

[0227] B: Prepolymer with repeating unit m = 8 (F = 9.1%)

[0228] C: Prepolymer with repeating unit m = 7 (F = 8.0%)

[0229] D: Prepolymer with repeating unit m = 6 (F = 8.6%)

[0230] E: Prepolymer with repeating unit m = 5 (F = 8.5%)

[0231] F: Prepolymer with repeating unit m = 4 (F = 8.1%)

[0232] G: Prepolymer with repeating unit m = 3 (F = 7.6%)

[0233] H: Prepolymer with repeating unit m = 2 (F = 6.6%)

[0234] I: unknown (F = 0.1%)

[0235] J: Prepolymer with repeating unit m = 1 (F = 4.6%)

[0236] K: unknown (F = 0.1%)

[0237] L: unknown (F = 0.2%)

[0238] M: Residual diol CHDM (F = 0.9%)

[0239] m was determined according to the weighted arithmetic mean.

[0240] 1 x F(m = 1) + 2 x F(m = 2) + — I- nx F(m = ri) m = -

[0241] F Prepolymer)

[0242] With F(Prepolymer) = 98.7%

[0243] 1 x 4.6 + 2 x 6.6 + 3 x 7.6 + 4 x 8.1 + 5 x 8.5 + 6 x 8.6 + 7 x 8.0 + 8 x 9.1 + 9 x 37.6 m ~98

[0244] = 6.4

[0245] The arithmetic mean of the repetition unit “m” for example 2 is at least 6.4.

[0246] DSC:

[0247] The glass transition temperature (T g ) was determined using differential scanning calorimetry (DSC) according to the standards DIN EN ISO 11357-1:2022-02 and DIN EN ISO 11357-2:2020-08, using a 2024PF30150a

[0248] - 41 -

[0249] Heating rate of 20 K / min measured under nitrogen, determined as the turning point in the second heating process.

[0250] 13 C-NMR spectroscopy:

[0251] The ratio of urethane to carbonate groups in the poly(urethane-co-carbonate)s was determined using 13The results were determined by C-NMR spectroscopy. For this purpose, approximately 20 mg of sample was dissolved in a suitable solvent (chloroform -dl or DMSO-d6) and measured on a Bruker AV III HD 600 NMR spectrometer at a measurement frequency of 151 MHz.

[0252] Measurement parameters:

[0253] Pulse program pulprog zgig30

[0254] Scan per increment NS: 256, 512 or 1024 (depending on the solubility of the sample)

[0255] Relaxation time between two scans: 4 days

[0256] The following section explains the evaluation of the urethane to carbonate group ratio using example 9 of a poly(urethane-co-carbonate) made from CHDM and MDI in the molar ratio of 1.25:1 (dioxine diisocyanate). Reference is made to Figure 5 (solvent used: DMSO-d6).

[0257] Assignment for the determination of urethane to carbonate from the 13 C-NMR spectrum urethane signal at 153.6 ppm (153.8 ppm with chloroform-dl as solvent)

[0258] Carbonate signal at 154.8 ppm (155.5 ppm with chloroform-dl as solvent)

[0259] The molar ratio is directly derived from the areas of the respective signals normalized to 100.

[0260] From the 13 The C-NMR spectrum in Figure 5 yields the following estimated molar ratio: Urethane = 88

[0261] Carbonate = 12

[0262] 'H-NMR spectroscopy:

[0263] The proportion of aromatic hydrocarbons (aromaticity) in poly(urethane-co-carbonate)s, implemented through the use of aromatic diisocyanates such as MDI and TDI, was determined by ¹H NMR spectroscopy. For this purpose, approximately 20 mg of sample was dissolved in a suitable solvent (chloroform-dl or DMSO-d6) and measured on a Bruker AV III HD 600 NMR spectrometer at a measurement frequency of 600.4 MHz. Measurement parameters:

[0264] Pulse program pulprog zg30 2024PF30150a

[0265] - 42 -

[0266] Scan per increment NS: 64

[0267] Relaxation time between two scans: 3 days

[0268] It was generally assumed that the poly(urethane-co-carbonate)s consist of polyurethane fractions of aromatic diisocyanate and diol, as well as polycarbonate fractions of diol. The aromaticity can be determined from the proportion of polyurethane composed of aromatic diisocyanate and diol by calculating the molecular weight of the polyurethane repeating unit and the proportion of aromatic hydrocarbons it contains. The determination of aromaticity is explained below using Example 9 (Figure 6).

[0269] For the poly(urethane-co-carbonate)s based on CHDM and MDI (Examples 8 to 13 and 15), the integral value (also called area, abbreviated F) of the chemical shift signal of 7.4 ppm (or 7.1 ppm) was chosen to assign the polyurethane from MDI and CHDM, as this signal can be attributed to 4 CH protons at the MDI. For the polycarbonate from CHDM, the integral value of the CH₂ signal at 3.7–4.1 ppm was chosen, as this signal can be attributed not only to the 4 CH₂ protons at the carbonate functionality but also to the 6 CH₂ protons of the polyurethane from MDI and CHDM. Therefore, the integral value of the signal at 3.7–4.1 ppm must be subtracted to obtain the integral for the 4 CH₂ protons of the polycarbonate from CHDM.

[0270] The proportion in mol% of aromatic polyurethane (PU) from MDI and CHDM is therefore calculated according to

[0271] F (7.4 ppm) 10Q

[0272] Aroma PU content (mol-%) = - - - „ . -

[0273] F(7, pp m ) F(3.7-4.1 ppm) - 6 - F (7 ' 4 4^ m)

[0274] 4 + 4

[0275] Using the integrals / areas determined from the 'H-NMR spectrum of example 9 in Figure 6

[0276] F(7.4 ppm) = 4

[0277] F(3.7-4.1 ppm) = 7.022 For example 9, the following aromatic polyurethane content was calculated: 2024PF30150a

[0278] - 43 -

[0279] Using the molecular weight of the repeating unit of the polyurethane from MDI and CHDM of 394.5 g / mol and the proportion of aromatics contained therein with a molecular weight of 152.2 g / mol, the proportion of aromatic groups can be calculated from the relative proportion of aromatic polyurethane from MDI and CHDM for the poly(urethane-co-carbonate)e based on CHDM and MDI (examples 8 to 13 and 15) according to the following formula:

[0280] 152.2 g / mol

[0281] Aromaticity (mol-%) = - - — - ; x Aroma. PU content (mol-%)

[0282] 394.5 g / mol

[0283] The following aromaticity was calculated for example 9:

[0284] “152.2 g / mol

[0285] Aromaticity (mol-%) = - - — - - x 80 = 31

[0286] 394.5 g / mol

[0287] It is clear to those skilled in the art that when using aromatic diisocyanates other than MDI (e.g. TDI) and diols other than CHDM (e.g. TCD-DM), other signals must be consulted to assign the polyurethane / polyurethane and polycarbonate and thus to determine the aromaticity.

[0288] Hydroxyl number:

[0289] The hydroxyl value (also called OH value) was determined titrimetrically by Currenta GmbH & Co. OHG in accordance with DIN EN ISO 4629-2. However, pyridine was used instead of the base A'-mcthyl-2-pyrrolidone used in the DIN EN ISO 4629-2 standard. The method used is defined under number 2011-0232602-92D at Currenta GmbH & Co. OHG, which can be requested from Currenta at any time.

[0290] NCO value:

[0291] The NCO content was determined titrimetrically according to DIN EN ISO 11909:2007-05.

[0292] Production of (hetero)aromatic urethanediol prepolymers (aroUDO) 2024PF30150a

[0293] - 44 -

[0294] Example 1: Reaction of CHDM (according to formula (1a), (1)) as diol component with MDI (according to formula (1a), (3)) as diisocyanate building block in a molar ratio of 1.1:1 (diol.Diisocyanate).

[0295] 103 g (714 mmol) of CHDM was placed in a flask equipped with a reflux condenser and dropping funnel. The apparatus was then purged of any traces of air and water by alternating evacuation and introduction of nitrogen. The CHDM was melted under nitrogen cover and atmospheric pressure at 200 °C and stirred for 30 minutes. 143 g (571 mmol) of MDI was added within a few seconds via the dropping funnel. After stirring for 10 minutes at 200 °C under nitrogen cover, followed by a 10-minute holding period at 220 °C and a 10-minute holding period at 240 °C, the mixture was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 29.2 mg KOH / g and a glass transition temperature Tg. g of 123 °C and a molecular weight M n of 6830 g / mol.

[0296] Example 2: Reaction of CHDM (according to formula (1a), (1)) as diol component with MDI (according to formula (1a), (3)) as diisocyanate building block in a molar ratio of 1.25:1 (diol.Diisocyanate).

[0297] 103 g (714 mmol) of CHDM was placed in a flask equipped with a reflux condenser and dropping funnel. The apparatus was then purged of any traces of air and water by alternating evacuation and introduction of nitrogen. The mixture was melted under nitrogen cover and atmospheric pressure at 200 °C and stirred for 30 minutes. 143 g (571 mmol) of MDI was added within a few seconds via the dropping funnel. After stirring for 10 minutes at 200 °C under nitrogen cover, followed by a five-minute holding period at 220 °C, the mixture was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 65.0 mg KOH / g and a glass transition temperature Tg. g of 105 °C and a molecular weight M n of 2940 g / mol.

[0298] Example 3: Reaction of CHDM (according to formula (1a), (1)) as diol component with MDI (according to formula (1a), (3)) as diisocyanate building block in a molar ratio of 1.5:1 (diol.Diisocyanate).

[0299] 115 g (797 mmol) of CHDM was placed in a flask equipped with a reflux condenser and dropping funnel. The apparatus was then purged of air and water by alternating evacuation and the introduction of nitrogen. The mixture was melted under nitrogen blanketing and atmospheric pressure at 200 °C and evaporated for 30 minutes. 2024PF30150a

[0300] - 45 - stirred. The addition of 133 g (531 mmol) of MDI was carried out within a few seconds via the dropping funnel. After 10 min of stirring at 200 °C under nitrogen blanketing, the mixture was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 114.2 mg KOH / g and a glass transition temperature T g of 80 °C and a molecular weight M nof 1650 g / mol.

[0301] Example 4: Reaction of CHDM (according to formula (1a), (1)) as diol component with MDI (according to formula (1a), (3)) as diisocyanate building block in a molar ratio of 2:1 (diol.Diisocyanate).

[0302] 121 g (839 mmol) of CHDM was placed in a flask equipped with a reflux condenser and dropping funnel. The apparatus was then purged of any traces of air and water by alternating evacuation and introduction of nitrogen. The mixture was melted under nitrogen cover and atmospheric pressure at 200 °C and stirred for 30 minutes. 105 g (420 mmol) of MDI was added via the dropping funnel within a few seconds. After stirring for 10 minutes at 200 °C under nitrogen cover, the mixture was stopped. A yellowish, transparent prepolymer was obtained with a total hydroxyl value of 194.0 mg KOH / g and a glass transition temperature Tg. g of 56 °C and a molecular weight M n of 780 g / mol.

[0303] Example 5: Reaction of CHDM (according to formula (1a), (1)) as diol component with MDI (according to formula (1a), (3)) as diisocyanate building block in a molar ratio of 3:1 (diol.Diisocyanate).

[0304] 140 g (971 mmol) of CHDM and 80 g (320 mmol) of MDI were placed in a flask with a reflux condenser. The apparatus was then purged of air and water by alternating evacuation and introduction of nitrogen. The mixture was melted under nitrogen blanketing and atmospheric pressure at 140 °C and stirred for 60 minutes. After 1 h, a sample was taken under nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 339.8 mg KOH / g and a molecular weight M n of 590 g / mol.

[0305] Example 6: Reaction of CHDM (according to formula (1a), (1)) as the diol component with TDI (according to formula (1a), (4)) as the diisocyanate building block in a molar ratio of 2:1 (diol.diisocyanate). 2024PF30150a

[0306] - 46 -

[0307] 82.8 g (574 mmol) of CHDM and 50 g (287 mmol) of TDI were placed in a flask with a reflux condenser. The apparatus was then purged of air and water traces by alternating evacuation and introduction of nitrogen. The mixture was melted under nitrogen blanketing and atmospheric pressure at 80 °C. Within 40 minutes, the mixture was heated to 130 °C. After 60 minutes at 130 °C, a sample was taken for NCO measurement in countercurrent nitrogen. The NCO value was 0%, and the reaction was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 245.5 mg KOH / g and a glass transition temperature Tg. g of 39 °C and a molecular weight M n of 710 g / mol.

[0308] Example 7: Reaction of TCD-DM (according to formula (1a), (2)) as diol component with MDI (according to formula (1a), (3)) as diisocyanate building block in a molar ratio of 2:1 (diol.Diisocyanate).

[0309] 160 g (815 mmol) of CHDM was placed in a flask equipped with a reflux condenser and dropping funnel. The apparatus was then purged of any traces of air and water by alternating evacuation and introduction of nitrogen. The mixture was melted under nitrogen cover and atmospheric pressure at 180 °C and stirred for 45 minutes. 102 g (408 mmol) of MDI was added via the dropping funnel within a few seconds. After stirring for 10 minutes at 180 °C under nitrogen cover, the mixture was stopped. A yellowish, transparent prepolymer was obtained with a total hydroxyl value of 191.7 mg KOH / g and a glass transition temperature Tg. g of 69 °C and a molecular weight M n of 860 g / mol.

[0310] Table 1: Comparison of the results of examples 1 to 7. 2024PF30150a

[0311] - 47 - Note: not exactly determinable, but at least greater than 5 kA: no analysis performed ber.: calculated (the number in brackets is the calculated OH number; formula for calculating the OH number: OH number

[0312] Production of (hetero)aromatic poly(urethane-co-carbonate)s (aroPUC) by polycondensation of previously prepared (hetero)aromatic urethanediol prepolymers (aroUDO) with diphenyl carbonate (PPC)

[0313] Example 8: Reaction of Example 1 as a UDO component with DPC as a carbonyl source in a molar ratio of 1:1.029 (UDO.DPC) in the presence of Katl.

[0314] 100.0 g (24.4 mmol, amount of substance determined from the calculated OH number) of Example 5 (calculated OH number: 27.4 mg KOH / g) and 5.37 g (25.1 mmol) of DPC, as well as 0.004 g (38 ppm, based on the starting materials, product from Example 1 and DPC) of Katl, were placed in a flask with a Vigreux column and distillation bridge. The apparatus was then purged of air and water traces by alternating evacuation and introduction of nitrogen. The mixture was melted under nitrogen blanketing and atmospheric pressure at 260 °C and stirred for 20 minutes. The pressure was then reduced to < 1 mbar within 60 minutes, and the mixture was stirred for a further 15 minutes. During this time, phenol was continuously removed. The process was then stopped. A brownish, transparent polymer with a M was obtained. w of 54,400 g / mol, a glass transition temperature T g of 117 °C and a molar carbonate to urethane ratio of 5:95.

[0315] Example 9: Reaction of Example 2 as a UDO component with DPC as a carbonyl source in a molar ratio of 1:1.028 (UDO.DPC) in the presence of Katl.

[0316] 100.0 g (57.9 mmol, amount of substance determined from the calculated OH number) of Example 6 (calculated OH number: 65.1 mg KOH / g) and 12.75 g (59.5 mmol) of DPC, as well as 0.004 g (35 ppm, based on the starting materials, product from Example 2 and DPC) of Katl, were placed in a flask with a Vigreux column and distillation bridge. The apparatus was then purged of air and water traces by alternating evacuation and the introduction of nitrogen. The mixture was melted under nitrogen blanketing and atmospheric pressure at 230 °C and stirred for 20 minutes. The temperature was then increased to 240 °C.

[0317] - 48 - increased and the pressure reduced to 250 mbar within 90 minutes. Phenol was continuously removed during this process. Subsequently, the temperature was increased to 250 °C and the pressure reduced to < 1 mbar within 30 minutes, and the mixture was stirred for a further 30 minutes. The reaction was then stopped. An orange, transparent polymer with a M was obtained. w of 76,900 g / mol, a glass transition temperature T g of 123 °C and a molar carbonate to urethane ratio of 12:88.

[0318] Example 10: Reaction of Example 3 as a UDO component with DPC as a carbony μ-que μ in a molar ratio of 1:1.028 (UDO.DPC) in the presence of cationic acid.

[0319] 100.0 g (107 mmol, amount of substance determined from the calculated OH number) of Example 3 (calculated OH number: 120.3 mg KOH / g) and 23.5 g (110 mmol) of DPC, as well as 0.004 g (32 ppm, based on the starting materials, product from Example 3 and DPC) of Katl, were placed in a flask with a Vigreux column and distillation bridge. The apparatus was then purged of air and water traces by alternating evacuation and the introduction of nitrogen. The mixture was melted under nitrogen blanketing and atmospheric pressure at 180 °C and stirred for 20 minutes. The pressure was then reduced to 250 mbar within 5 minutes, the temperature to 200 °C, and the mixture was stirred for a further 25 minutes. The mixture was then stirred for 10 minutes at 210 °C, for 10 minutes at 220 °C, for 5 minutes at 230 °C, and for 10 minutes at 240 °C. During this process, phenol was continuously removed.The pressure was then reduced to < 1 mbar within 30 minutes, and the mixture was stirred for a further 60 minutes. The reaction was then stopped. An orange, transparent polymer with a molecular weight of M was obtained. w of 174,700 g / mol, a glass transition temperature T g of 120 °C and a molar carbonate to urethane ratio of 20:80.

[0320] Example 11: Reaction of Example 4 as a UDO component with DPC as a carbonyl source in a molar ratio of 1:1.023 (UDO.DPC) in the presence of Katl.

[0321] 92 g (171 mmol, amount of substance determined from the calculated OH number) of Example 4 (calculated OH number: 208.3 mg KOH / g) and 37.5 g (175 mmol) of DPC, as well as 0.005 g (38 ppm, based on the starting materials, product from Example 4 and DPC) of Katl, were placed in a flask with a Vigreux column and distillation bridge. The apparatus was then purged of air and water traces by alternating evacuation and the introduction of nitrogen. The mixture was melted under nitrogen blanketing and atmospheric pressure at 180 °C and stirred for 20 minutes. The pressure was then reduced to 100 mbar within 20 minutes, and the mixture was stirred for a further 20 minutes. Then the 2024PF30150a

[0322] - 49 -

[0323] The mixture was stirred for 10 minutes at 190 °C, for 10 minutes at 200 °C, for 5 minutes at 210 °C, for 5 minutes at 220 °C, for 5 minutes at 230 °C, and for 5 minutes at 240 °C. During this time, phenol was continuously removed. The pressure was then reduced to < 1 mbar within 30 minutes, and the mixture was stirred for a further 60 minutes. The process was then stopped. An orange, transparent polymer with a M was obtained. w of 84,300 g / mol, a glass transition temperature T g of 121 °C and a molar carbonate to urethane ratio of 33:67.

[0324] Example 12: Reaction of Example 5 as UDO component with DPC as carbonyl source in a molar ratio of 1:1.050 (UDO.DPC) in the presence of Cat2 and Cat3.

[0325] 75 g (222 mmol, amount of substance determined from the calculated OH number) of Example 5 (calculated OH number: 332.1 mg KOH / g), 50 g (233 mmol) of DPC, and 32 pL (corresponding to 0.16 mg, 1.3 ppm based on the starting materials Example 5 and DPC) of Category 2, as well as 125 pL (corresponding to 12.5 mg, 100 ppm based on the starting materials Example 5 and DPC) of Category 3, were placed in a flask with a Vigreux column and distillation bridge. The apparatus was then purged of air and water by alternately evacuating and introducing nitrogen. The mixture was melted under nitrogen blanketing and atmospheric pressure at 150 °C and stirred for 10 minutes. The mixture was then stirred under nitrogen blanketing and normal pressure for 10 minutes at 180 °C, for 10 minutes at 200 °C, for 10 minutes at 220 °C, and for 100 minutes at 240 °C. The pressure was then reduced to < 1 mbar within 90 minutes, and the mixture was stirred for a further 60 minutes.Phenol was continuously removed. The reaction was then stopped. A yellowish, transparent polymer with a molecular weight was obtained. w of 56,000 g / mol, a glass transition temperature T g of 91 °C and a molar carbonate to urethane ratio of 51 :49.

[0326] Example 13: Reaction of Example 6 as a UDO component with DPC as a carbonyl source in a molar ratio of 1:1.049 (UDO.DPC) in the presence of Katl.

[0327] 75 g (162 mmol, amount of substance determined from the calculated OH number) of Example 6 (calculated OH number: 242.6 mg KOH / g) and 36.47 g (170 mmol) of DPC, as well as 0.004 g (36 ppm, based on the starting materials Example 6 and DPC) of Katl, were placed in a flask with a Vigreux column and distillation bridge. The apparatus was then purged of air and water traces by alternately evacuating and introducing nitrogen. The mixture was melted under nitrogen blanketing and atmospheric pressure at 180 °C and stirred for 20 minutes. The pressure was then reduced to 100 mbar within 5 minutes. 2024PF30150a

[0328] The pressure was reduced to -50 and the mixture was stirred for a further 60 minutes. Then the mixture was stirred for 10 minutes at 190 °C, for 10 minutes at 200 °C, for 5 minutes at 210 °C, for 5 minutes at 220 °C, for 5 minutes at 230 °C, and for 10 minutes at 240 °C. During this time, phenol was continuously removed. Subsequently, the pressure was reduced to <1 mbar within 25 minutes and the mixture was stirred for a further 70 minutes. The reaction was then stopped. An orange, transparent polymer with a M was obtained. w of 160,700 g / mol, a glass transition temperature T g of 106 °C and a molar carbonate to urethane ratio of 37:63.

[0329] Example 14: Reaction of Example 7 as a UDO component with DPC as a carbonyl source in a molar ratio of 1:1.029 (UDO.DPC) in the presence of Katl.

[0330] 90 g (140 mmol, amount of substance determined from the calculated OH number) of Example 7 (calculated OH number: 174.5 mg KOH / g) and 30.74 g (144 mmol) of DPC, as well as 0.004 g (33 ppm, based on the starting materials Example 7 and DPC) of Katl, were placed in a flask with a Vigreux column and distillation bridge. The apparatus was then purged of air and water traces by alternately evacuating and introducing nitrogen. The mixture was melted under nitrogen blanketing and atmospheric pressure at 180 °C and stirred for 20 minutes. The pressure was then reduced to 100 mbar within 5 minutes. The mixture was then stirred for 10 minutes at 190 °C, for 20 minutes at 200 °C, for 20 minutes at 210 °C, for 10 minutes at 220 °C, for 5 minutes at 230 °C, and for 5 minutes at 240 °C. During this time, phenol was continuously removed. The pressure was then reduced to < 1 mbar within 25 minutes, and the mixture was stirred for a further 50 minutes.The approach was then discontinued. An orange, transparent polymer with an M was obtained. w of 195,300 g / mol, a glass transition temperature T g of 125 °C and a molar carbonate to urethane ratio of 35:65.

[0331] Table 2: Comparison of the results of examples 8 to 14. 2024PF30150a

[0332] - 51 -

[0333] * By bending the solidified melt by hand, a first impression could be gained. The material is described as "ductile" if it could not be broken when bent. Otherwise, it would be described as "brittle".

[0334] Production of (hetero)aromatic poly(urethane-co-carbonate)e (aroPUC) - One-Pot

[0335] Example 15: Reaction of CHDM (according to formula (1a), (1)) as diol component with MDI (according to formula (1a), (3)) as diisocyanate building block and DPC as carbonyl source in the molar ratio of 2:1:1.05 (diol.Diisocyanate.DPC) in the presence of Catl.

[0336] 46.1 g (320 mmol) of CHDM, 40.0 g (160 mmol) of MDI, 36.0 g (168 mmol) of DPC, and 0.004 g (33 ppm, based on the starting materials CHDM, MDI, and DPC) of Katl were placed in a flask equipped with a Vigreux column and distillation bridge. The mixture was then stirred under nitrogen blanketing and atmospheric pressure for 15 minutes at 130 °C, 10 minutes at 140 °C, 50 minutes at 150 °C, 50 minutes at 170 °C, and 10 minutes at 180 °C. The pressure was then reduced to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar within 15 minutes, and the mixture was stirred for a further 60 minutes. Finally, the mixture was stirred for 5 minutes at 210 °C and for 5 minutes at 240 °C. The pressure was then reduced to < 1 mbar within 10 minutes, and the mixture was stirred for a further 60 minutes. Afterward, the process was stopped. A brownish, transparent polymer with a M was obtained. w of 58,200 g / mol and a glass transition temperature Tg of 112 °C.

[0337] Production of (hetero)aromatic poly(urethane-co-carbonate)e (aroPUC) - Sequential One-Pot

[0338] Example 16: Reaction of TCD-DM (according to formula (1a), (2)) as diol component with MDI (according to formula (1a), (3)) as diisocyanate building block and subsequent reaction with DPC as carbonyl source in the molar ratio of 2:1:1.027 (diol.Diisocyanate.DPC) with addition of Catl.

[0339] 57.4 g (292 mmol) of TCD-DM was placed in a flask equipped with a Vigreux column, distillation bridge, and dropping funnel. The apparatus was then purged of air and water by alternating evacuation and introduction of nitrogen. The TCD-DM was melted under nitrogen blanketing and atmospheric pressure at 180 °C and stirred for 30 minutes. 36.6 g (146 mmol) of MDI was added according to 2024PF30150a.

[0340] - 52 - within a few seconds via the dropping funnel. The mixture was stirred for 10 minutes at 180 °C. Subsequently, 32.1 g (150 mmol) of DPC and 0.004 g (32 ppm, based on the starting materials TCD-DM, MDI, and DPC) of Katl were added in a nitrogen countercurrent. The mixture was then stirred for 20 minutes at 180 °C under a nitrogen atmosphere. The pressure was then reduced to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar within 15 minutes, and the mixture was stirred for a further 30 minutes. The mixture was then successively heated in 10 °C increments to 240 °C within 90 minutes and stirred for 10 minutes at 240 °C. The pressure was then reduced to < 1 mbar within 15 minutes, and the mixture was stirred for a further 30 minutes. The reaction was then stopped. An orange, transparent polymer with a M was obtained. w of 102,100 g / mol, a glass transition temperature T gof 129 °C, a molar carbonate to urethane ratio of 33:67 and an aromaticity of 17 mol-%.

Claims

2024PF30150a Patent claims:

1. Thermoplastic poly(urethane-co-carbonate), comprising structures of formulas (I) and (II) (I), where each R 1 in formula (I) each independently represents an aliphatic group with 4 to 18 carbon atoms, which has at least one cycle and where this cycle may optionally contain at least one heteroatom, and where each R 2Formula (II) each independently represents a bridging aromatic structure with 6 to 18 carbon atoms, wherein the wavy lines in formulas (I) and (II) each represent the connection of the structures of formulas (I) and (II) to the chain of poly(urethane-co-carbonate), and wherein at least a part of the structures of formulas (I) and (II) are each directly linked to each other to form a urethane group, and at least a further part of the structures (I) are directly linked to at least one further structure of formula (I) to form a carbonate group, characterized in that the thermoplastic poly(urethane-co-carbonate) has > 1 mol% to < 99 mol% carbonate groups, based on the sum of the carbonate and urethane groups in the poly(urethane-co-carbonate), wherein the mol% of carbonate and urethane groups are determined by 13C-NMR spectroscopy is determined, and that the thermoplastic poly(urethane-co-carbonate) has a weight average molar mass of at least 40,000 g / mol and that the thermoplastic poly(urethane-co-carbonate) does not have structures of the general formula (II*) 2024PF30150a - 54 - exhibits, in which R is not an aromatic group.

2. Thermoplastic poly(urethane-co-carbonate) according to claim 1, comprising structural formula (III) where each R 1 the meanings mentioned in formula (I), whereby the group enclosed by the round brackets -CFF-R'-CFF- also partially represents R independently of each other. 6 can stand, provided that at least part of the structures is -CFF-R'-CFF-, and R 6for an aliphatic alkyl group with 4 to 20 carbon atoms, which can be linear, branched or have at least one cycle, wherein the at least one cycle can have at least one heteroatom, where R 6 , if R 6 has at least one cycle, is not integrated into structure (III) via a -CH2 group on at least one side, and each R 2 which has the meaning mentioned in formula (II) and m is the arithmetic mean of the repetition units and is a number > 1.5 and the wavy lines represent the connection of the structure of formula (III) to the chain of poly(urethane-co-carbonate).

3. Thermoplastic poly(urethane-co-carbonate) according to claim 1 or 2, characterized in that R 1 represented independently of each other in formula (I) and in formula (III) respectively by formula (1) or formula (2), where the positions marked with the stem in formulas (1) and (2) are the positions where the CIT groups shown in formula (I) and formula (III) are located, respectively. 2024PF30150a - 55 - 4. Thermoplastic poly(urethane-co-carbonate) according to one of claims 1 to 3, characterized in that the structure R 2 represented independently of each other in formula (II) or formula (III) by formula (3) or formula (4), where each R 3 in formula (3) independently represents a methyl or ethyl group, p represents 0, 1, or 2, and q represents 0 or 1, and each R 3in formula (4) independently represents a methyl or ethyl group and p represents 0, 1, or 2 and d represents 0 or 1 independently, and wherein the positions marked with the stem in formulas (3) and (4) are the positions where the nitrogen atoms shown in formula (II) and formula (III) are located, respectively.

5. Thermoplastic poly(urethane-co-carbonate) according to one of claims 1 to 4, characterized in that the thermoplastic poly(urethane-co-carbonate) has < 39 mol-% aromatic groups, wherein this quantity refers to the total amount of aliphatic and aromatic groups.

6. Thermoplastic poly(urethane-co-carbonate) according to any one of claims 2 to 5, characterized in that the thermoplastic poly(urethane-co-carbonate) does not contain any groups R 6 exhibits.

7. Process for the production of a thermoplastic poly(urethane-co-carbonate), comprising the process steps (i) Implementation of at least one aliphatic diol of formula (1a) HO — CH2 1 — R 1 - CH, — OH / T , (1a), where each R 1 in formula (a) each independently represents an aliphatic group with 4 to 18 carbon atoms, which has at least one cycle and where this cycle may optionally contain at least one heteroatom, 2024PF30150a - 56 - with at least one aromatic diisocyanate of formula (Ila) OCN — R 2 — NCO (Ila), where R 2 in the formula (Ila) stands for a bridging aromatic structure with 6 to 18 carbon atoms, to a prepolymer and (ii) Reaction of the prepolymer obtained from process step (i) with a diaryl carbonate in the presence of at least one catalyst to obtain the poly(urethane-co-carbonate), characterized in that in process step (i) the molar ratio of all diols used to all diisocyanates used is 5.0:1.0 to 1.01:1.0 and that, in addition to the diisocyanates of formula (Ila), no non-aromatic diisocyanates are used.

8. Method according to claim 7, characterized in that in process step (i) at least one diol of formula (X) is also used with HO-R 6 -OH (X), where each R 6 for an aliphatic alkylene group having 4 to 20, preferably 5 to 18, particularly preferably 6 to 16 carbon atoms, which may be linear or branched or may have at least one cycle, wherein the at least one cycle may have at least one heteroatom, and wherein, if R6 has at least one cycle, and at least one OH group does not belong to a primary alcohol group.

9. Method according to claim 7 or 8, characterized in that R 1 represented in formula (1a) by formula (1) or formula (2), 2024PF30150a - 57 - where the positions marked with the stem in formulas (1) and (2) are the positions where the CFF groups shown in formula (1a) are located.

10. Method according to one of claims 7 to 9, characterized in that the structure R 2 represented in formula (Ila) by one of formulas (3) or (4), where each R 3 in formula (3) independently represents a methyl or ethyl group, p represents 0, 1, or 2, and q represents 0 or 1, and each R 3in formula (4) independently represents a methyl or ethyl group and p represents 0, 1, or 2 and d represents 0 or 1 independently, and wherein the positions marked with an asterisk in formulas (3) and (4) are the positions where the nitrogen atoms shown in formula (Ila) are located.

11. Method according to one of claims 7 to 10, characterized in that no further diols and / or diisocyanates are used other than the diols of formula (1a) and / or the diisocyanates of formula (1a).

12. Thermoplastic poly(urethane-co-carbonate) according to any one of claims 1 to 6, produced according to the method according to any one of claims 7 to 11.

13. Urethanediol prepolymer produced by process step (i) of the process according to any one of claims 7 to 11.

14. Urethanediol prepolymer according to claim 13, comprising a structure of formula (V) 2024PF30150a - 58 - where each R 1 in formula (V) each independently represents an aliphatic group with 4 to 18 carbon atoms, which has at least one cycle and where this cycle may optionally contain at least one heteroatom, and where the group enclosed by the round brackets -CH2-R'-CH2- also partially represents R each independently 6 can be, provided that at least part of the structures is -CH2-R'-CH2-, and R 6 for an aliphatic alkylene group with 4 to 20 carbon atoms, which can be linear, branched or have at least one cycle, wherein the at least one cycle can have at least one heteroatom, and wherein R 6 , if R 6 has at least one cycle, is not incorporated into the structure (V) via a -CH2 group on at least one side, and where each R 2of formula (V) each independently represents a bridging aromatic structure with 6 to 18 carbon atoms and where m is the arithmetic mean of the repeating units and is a number > 1.

5.

15. Urethanediol prepolymer according to claim 13, comprising a structure of formula (Va) where each R 1 in formula (Va) each independently represents an aliphatic group with 4 to 18 carbon atoms, which has at least one cycle and wherein this cycle may optionally contain at least one heteroatom, and wherein each R 2 of the formula (Va) each independently represents a bridging aromatic structure with 6 to 18 carbon atoms and where m is the arithmetic mean of the repeating units and is a number > 1.5.

Images