Production of thermoplastic poly(urethane- co-carbonate)s based on high-viscosity (hetero)cycloaliphatic urethanediol prepolymers

Abstract

A method is described for producing thermoplastic poly(urethane-co-carbonate)s via high-viscosity urethanediol prepolymers. The transparent thermoplastic poly(urethane-co-carbonate)s have high glass transition temperatures of ≥ 110°C and molar masses in a range of Mw of at least 40 000 g / mol to preferably 190 000 g / mol with viscous characteristics at room temperature. These polymers can be processed to give mouldings in common plastification processes.

Description

[0001] Production of thermoplastic poly(urethane carbonate)s based on highly viscous (heterolcycloaliphatic urethanediol prepolymers

[0002] The present invention relates to an improved process for the production of thermoplastic poly(urethane-co-carbonate) via highly viscous urethanediol prepolymers, the urethanediol prepolymers themselves and the thermoplastic poly(urethane-co-carbonate)s produced therefrom.

[0003] Aromatic polycarbonates are known for their excellent properties in terms of mechanical and optical properties, heat resistance, and weathering stability. However, the presence of aromatic groups also imposes certain limitations on these properties, such as transmission, birefringence, and yellowing tendencies. Furthermore, depending on the manufacturing process, a large amount of phenol is produced as condensate, which requires complex collection and processing. Aliphatic polycarbonates exhibit improved properties in the aforementioned areas that still require improvement, as well as in chemical resistance. However, they generally have low glass transition temperatures and, consequently, lower heat resistance.There are therefore efforts to provide polymers that combine the positive properties of aromatic polycarbonates and aliphatic polycarbonates, but at the same time do not exhibit the negative properties and generate as little phenol as possible during production.

[0004] In EP 2 883 898 A1, an aliphatic polycarbonate is blended with a polyurethane. By forming an IPN (interpenetrating polymer network), the mechanical properties of the aliphatic polycarbonate were improved. The aliphatic polycarbonate is a polypropylene carbonate or polyethylene carbonate. It therefore contains linear aliphatic structures, which generally result in low glass transition temperatures (approx. 25-45 °C). Furthermore, the examples in this document use exclusively aromatic diisocyanates. These generally increase the glass transition temperature of the described blends, but their aromatic groups also result in the disadvantages mentioned above (in particular, yellowing tendency, poorer transmission, and birefringence).

[0005] WO 2013 / 016331 A2 describes a polyurethane composition comprising an aliphatic polycarbonate structure. These also contain linear ethylene oxide or propylene oxide chains and have 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 in turn reacted with aromatic diisocyanates. Here, too, the aforementioned disadvantages arise from the introduction of aromatic groups into the polymer structure.

[0006] EP 1 700 877 A1 describes poly(urethane carbonate) polyols which are 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 together with the unreacted, excess diol to obtain the poly(urethane carbonate) polyol having a relatively low molar mass of approximately 1 000 to 2 000 g / mol (as can be seen from the OH numbers). The resulting polyols have glass transition temperatures below 0 °C. They are first reacted with an aromatic diisocyanate to form a prepolymer and then processed into a cast elastomer with the addition of a linear diol. Since this document therefore concerns the preparation of cast elastomers, the glass transition temperatures of the polyols are not the focus orto the ranges required for cast elastomers. These differ significantly from the preferred ranges for thermoplastic polycarbonate compositions.

[0007] Based on the prior art, the object was therefore to overcome at least one disadvantage, preferably all of the disadvantages, of the prior art. In particular, the object of the present invention was to provide a polymer which has glass transition temperatures of at least 110 °C. The polymer should also have good optical properties (in particular transparency). At the same time, the polymer should preferably also have high heat resistance. Likewise preferably, the polymer should be processable using the plasticizing methods commonly used for aromatic polycarbonate, e.g. injection molding, (co)extrusion, blow molding, and deep drawing. For this purpose, it is particularly advantageous if the thermoplastic polymer is amorphous. Likewise preferably, the thermoplastic polymer should have good mechanical properties, for example properties comparable to those of aromatic polycarbonate.Particularly preferably, the thermoplastic polymer should exhibit at least a ductile fracture at room temperature. Likewise, the production of the thermoplastic polymer should produce lower amounts of phenol than aromatic polycarbonates.

[0008] The applicant has already proposed the subject matter of European patent application No. 23217149.6, which has not yet been published, as a solution to the aforementioned problems. The poly(urethane-co-carbonate)s described therein, together with their preparation processes, already solve at least one of the aforementioned problems, preferably all of them.

[0009] The applicant has now surprisingly found that the production process for the polymers can be further optimized by working in a range with an even smaller excess of diol in relation to the diisocyanate, namely in a molar ratio of all diols used to all diisocyanates used of 1.30: 1.0 to 1.01: 1.0, particularly preferably 1.27: 1.0 to 1.05: 1.0, very particularly preferably 1.25: 1.0 to 1.10: 1.0.

[0010] This results in a highly viscous prepolymer. This has the further advantage that, due to its high molecular weight and the resulting low proportion of terminal OH groups, less distillate is released in the form of phenol during the polycondensation reaction. Preferably, less than 15 wt.% of distillate is released in the form of phenol, based on all feedstocks (without catalyst).

[0011] The invention thus relates to a process for producing a thermoplastic poly(urethane-co-carbonate), comprising the process steps

[0012] (i) Reaction of at least one aliphatic diol of formula (la)

[0013] HO — CH2— R 1 - CH2— OH (Ia) where each R 1 in the formula (Ia) each independently represents an aliphatic group having 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 aliphatic diisocyanate of the formula (Ila) where R 2in formula (Ila) represents a bridging aliphatic structure having 6 to 18 carbon atoms, wherein said bridging structure has at least one cycle and said cycle may optionally contain at least one heteroatom and wherein the bridging structure is linked to the nitrogen atoms shown in structure (Ila) in each case via a secondary or tertiary carbon atom, to a prepolymer and (ii) reacting 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 1.30: 1.0 to 1.01: 1.0, particularly preferably 1.27: 1.0 to 1.05: 1.0, very particularly preferably 1.25: 1.0 to 1.10: 1.0.

[0014] The invention also relates to a thermoplastic poly(urethane-co-carbonate) comprising structures of the formulas (I) and (II), where each R 1 in formula (I) each independently represents an aliphatic group having 4 to 18 carbon atoms, which has at least one cycle and this cycle may optionally contain at least one heteroatom, and where each R 2of formula (II) each independently represents a bridging aliphatic structure having 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 linked to the nitrogen atoms shown in structure (II) via a secondary or tertiary carbon atom, wherein the wavy lines in formula (I) and (II) each represent the linkage of the structures of formulas (I) and (II) into the chain of the poly(urethane-co-carbonate), and wherein at least some of the structures of formula (I) and (II) are each directly linked to one another to form a urethane group, and at least a further part of the structures (I) is directly linked to one another to form a carbonate group with at least one further structure of formula (I), characterized in thatthat the thermoplastic poly(urethane-co-carbonate) has > 1 mol-% to < 15 mol-% carbonate groups, based on the sum of the carbonate and urethane groups in the poly(urethane-co-carbonate), where the mol-percentages of carbonate and urethane groups are above, 13 C-NMR spectroscopy, and that the thermoplastic poly(urethane-co-carbonate) has a weight-average molecular weight of at least 40,000 g / mol. The thermoplastic poly(urethane-co-carbonate) is preferably produced by the process of the invention.

[0015] According to the invention, the term “poly(urethane-co-carbonate)” is used to describe a polymer having the features according to the invention.

[0016] R 1 is defined as “an aliphatic group having 4 to 18 carbon atoms, which has at least one cycle and this cycle may optionally contain at least one heteroatom”. R 1thus includes "cycloaliphatic" and "heterocycloaliphatic groups." "Cycloaliphatic" in the sense of the present invention preferably means that the group is composed only of carbon atoms and hydrogen atoms. Here and elsewhere, according to the invention, "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 bond 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 1has at least one cycle. The two carbon atoms from which the two hydrogen atoms have been removed can be arbitrary, ie, any part of the cycle or of the linear alkylene group, if present. In addition, the cycloalkylene group according to the present invention can also be linked to at least one other cycloaliphatic ring via a bridging structure or can also be condensed. A cycloaliphatic group can also have one or more double bonds. The number of carbon atoms of the aliphatic group R 1 is here and in all other places where the polymer, the process and the prepolymer are described, preferably 6 to 18, more preferably 6 to 10 carbon atoms.

[0017] 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 connected 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 heteroatom.

[0018] In the context of the present invention, the term "alkylene" or "alkylene group" preferably refers, unless otherwise stated, to a bridging alkane structure from which two hydrogen atoms have been removed from different carbon atoms. 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 do not necessarily have to be adjacent. An alkylene group can be linear or branched. It is saturated. If the alkylene group comprises only one carbon atom, it is a methylene group (-CH2-), which is linked to the rest of the molecule via two single bonds.The alkylene group preferably comprises methylene, ethylene, n-propylene, 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.

[0019] It is obvious to the person skilled in the art that, if R 1 in the diol of formula (la) or R 2in the diisocyanate of formula (Ila) has more than one cycle, one or more carbon atoms of the claimed 4 to 18 or 6 to 18 carbon atoms can also be part of two or more cycles at the same time.

[0020] The molar ratio of all diols used, in particular the (cyclo)aliphatic diol of formula (Ia), to all diisocyanates used, in particular the (cyclo)aliphatic diisocyanate of formula (Ila), can influence, among other things, the resulting proportion of carbonate groups and urethane groups in the poly(urethane-co-carbonate).

[0021] In process step (i), at least one aliphatic diol of formula (Ia) is used. It is clear that only aliphatic diol of formula (Ia) can be used as the diol. This can be one or more aliphatic diols of formula (Ia). In particular, it is clear that if R 1has 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 (Ia) each independently represents an aliphatic group having 4 to 18 carbon atoms, which has at least one cycle and which may optionally contain at least one heteroatom, preferably oxygen.

[0022] The process according to the invention is most preferably characterized in that R 1 in formula (la) is represented by formula (1) or formula (2), where the positions marked with the star symbol in formulas (1) and (2) are the positions at which the CH2 groups shown in formula (1a) are located.

[0023] In addition to the aliphatic diol of formula (Ia), one or more further diol(s) can also be used in process step (i). It is preferred that the one or more further diol(s) in process step (i) be used in an amount of at most 75 mol%, particularly preferably at most 60 mol%, likewise preferably at most 40 mol%, likewise particularly preferably at most 25 mol%, likewise preferably at most 10 mol%, and very particularly preferably at most 5 mol%, based on all diols used. Extremely preferably, no further diol is used besides the at least one aliphatic diol of formula (Ia).

[0024] The one or more further diol(s) in process step (i) is preferably at least one diol of the formula (X)

[0025] HO-R 6 -OH (X), where each R 6represents 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, when 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 that it is a secondary or tertiary alcohol function. Preferably, both of the OH groups are not incorporated into formula (X) via a CFF group. It is understood that "incorporated via..." means that the corresponding incorporating group is part of formula (X).

[0026] However, it is preferred that no diol containing an ether group be used in process step (i) of the process according to the invention. Likewise, it is preferred that no diol containing an ester group be used in process step (i) of the process according to the invention. In particular, no polyether polyols and / or polyester polyols are used in process step (i) of the process according to the invention. Particularly preferred further diols can also be derived by the person skilled in the art from the preferences mentioned later for formula (li).

[0027] 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 a "further" compound. The compound referred to as "at least" is mandatory, and the further compound(s) may be present in addition. Accordingly, the skilled person can also determine the ratios of diols to diisocyanates.

[0028] In process step (i), at least one aliphatic diisocyanate of formula (IIa) is further used. It is evident that this aliphatic diisocyanate of formula (IIa) can be used as the sole diisocyanate. R 2 in formula (Ila) prefers the above-mentioned meanings of R 2 to formula (II). In particular, R 2 for a Ce to Ci8 cycloalkylene group according to the preferred definition given above, taking into account the limitation as to R 2The process according to the invention is most preferably characterized in that the structure R 2 in formula (Ila) is represented by one of the formulas (3) to (8),

[0029] where the positions marked with the star in formulas (3) to (8) are the positions at which the nitrogen atoms shown in formula (IIa) are located, and 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 wherein each R 3 in formula (5) independently represents a methyl or ethyl group and p represents 0, 1, or 2.

[0030] Particular preference is given in process step (i) of the process according to the invention to at least one aliphatic diol of the formula (Ia), where R 1 of formula (1) and / or (2), and structures of formula (IIa), in which R 2is 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 is preferred in which at least 80 mol% of the structures are 4,4'-isomers and the remainder are 2,4'- or 2,2'-isomers.

[0031] In addition to the aliphatic diisocyanate of formula (Ila), one or more further diisocyanates can also be used in process step (i). It is preferred that the one or more further diisocyanates in process step (i) are used in an amount of not more than 75 mol%, particularly preferably not more than 60 mol%, likewise preferably not more than 40 mol%, likewise particularly preferably not more than 25 mol%, likewise preferably not more than 10 mol%, and very particularly preferably not more than 5 mol%, based on all diisocyanates used. "Up to" here means that the respective stated limit is included in the described range. Extremely preferably, no further diisocyanate is used in addition to the at least one aliphatic diisocyanate of formula (Ila). The one or more further diisocyanates in process step (i) are preferably at least one diisocyanate of formula (Xi)

[0032] OCN-R 7-NCO (Xi), where each R 7 in the formula (Xi) for

[0033] - a linear alkylene group with 4 to 12 carbon atoms,

[0034] - a cycloaliphatic group having 5 to 20, preferably 7 to 18 carbon atoms, but the bonding of the structure R 7 to at least one of the nitrogen atoms shown in structure (Xi) via a primary carbon atom, or

[0035] - an aromatic group having 6 to 18 carbon atoms. Particularly preferred further diisocyanates can also be derived by the person skilled in the art from the preferences for formula (III) mentioned later.

[0036] In addition to the diols with R 1 according to formula (1) and / or (2) and diisocyanates with R 2 according to at least one of the formulas (3) to (8), in particular according to formula (3), no further diol and / or diisocyanate is used.

[0037] In process step (i) according to the invention, a prepolymer is prepared. The prepolymer, preferably prepared by process step (i), is also the subject of the present invention.

[0038] According to the invention, a prepolymer is understood as 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.

[0039] The OH-terminated prepolymer preferably comprises the structural formula (III) where each R 1 has the meanings given for formula (I), where the group enclosed by the round brackets -CFE-R'-CFE- also partly independently of one another represents R 6 can stand, provided that at least part of the structures is - CFE-R'-CFE-, and R 6represents an aliphatic alkylene group having 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 bound into the structure (III) via a CH2 group at least on one side, preferably on both sides, and each R 2 has the meanings given for formula (II), and the expression R 2 / R 7 means that the group R 2 at least partly also independently of each other for R 7 provided that at least some of the groups R 2 is, and R 7 for

[0040] - a linear alkylene group with 4 to 12 carbon atoms,

[0041] - a cycloaliphatic group having 5 to 20 carbon atoms, but the bonding of the structure R7 to at least one of the nitrogen atoms shown in structure (III) via a primary carbon atom or

[0042] - an aromatic group having 6 to 18 carbon atoms and m is the arithmetic mean of the repeating units and is a number > 4.0, preferably

[0043] > 4.5, particularly preferably > 4.75, most preferably > 5.0. The arithmetic mean of the repeating units m is preferably a number < 25.0, particularly preferably < 21.0, most preferably < 10.0.

[0044] This prepolymer is further preferably an OH-terminated urethane prepolymer with a build-up factor as defined below, having a structure of the formula (IIIa) where each R 1in the formula (IIIa) each independently represents an aliphatic group having 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 formula (IIIa) stands for a bridging aliphatic structure having 6 to 18 carbon atoms, wherein said bridging structure has at least one cycle and wherein said cycle may optionally contain at least one heteroatom and wherein the bridging structure is linked to the nitrogen atoms shown in structure (IIIa) in each case via a secondary or tertiary carbon atom, wherein m is the arithmetic mean of the repeating units and is a number > 4.0, preferably > 4.5, particularly preferably > 4.75, very particularly preferably > 5.0. The arithmetic mean of the repeating units m is preferably a number < 25.0, particularly preferably < 21.0, very particularly preferably < 10.0.

[0045] Preferably, only diols of formula (Ia) and diisocyanates of formula (Ila) are used.

[0046] A urethane prepolymer contains the urethane group -NH-CO-O-. The build-up factor, designated "m" in formulas (III) and (IIIa), indicates the number of diisocyanate building blocks in the prepolymer. It is the arithmetic mean of the repeating units found in the square brackets. The build-up factor is limited by the fact that it is a "prepolymer," i.e., a reactive building block with terminal OH groups as reactive functionalities.

[0047] The person skilled in the art can determine the arithmetic mean of repeat units m using known methods. In particular, m can be determined by gel permeation chromatography; preferably, the gel permeation chromatography method described later is used for this purpose. This yields different peaks, which can be assigned to corresponding oligomers based on their molecular weight. If the peaks are not clearly separated (particularly in the case of longer-chain oligomers), the peaks can preferably be subdivided at the nadir between two peaks. If no nadir is measured, the tailing of the peak is preferably still counted as part of the corresponding repeat unit of the maximum (see also the experimental section and Figures 2 and 4). The weighted arithmetic mean of the repeat unit m can be calculated from the areas.

[0048] A particularly preferred OH-terminated urethane prepolymer according to the invention is one in which R 1 is represented by

[0049] (1) or (2), wherein the positions marked with the star in formulas (1) and (2) are the positions at which the CH2 groups shown in formulas (III) and (IIIa) are located, respectively, and R 2 is represented by one of the formulas (3) to (8), where the positions marked with the star in formulas (3) to (8) are the positions at which the nitrogen atoms shown in formula (III) and (IIIa) are located, respectively, and 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 wherein each R 3 in formula (5) independently represents a methyl or ethyl group and p represents 0, 1, or 2.

[0050] "OH-terminated" means that OH groups are present at both chain ends of the urethane prepolymer. The prepolymer can therefore also be referred to as "urethanediol." The person skilled in the art can determine the amount of reactive OH groups by known methods. In particular, by titration, the concentration of OH groups can be determined as the hydroxyl number (also called OH number) in mg KOH / g. The OH number of the urethane prepolymers is preferably between 14 and 85 mg KOH / g, more preferably between 16 and 80 mg KOH / g, particularly preferably between 18 and 75 mg KOH / g, and most preferably between 20 and 70 mg KOH / g, with the OH number preferably being determined by titration in accordance with DIN EN ISO 4629-2, where "in accordance" means that pyridine is used instead of the base '-methyl-2-pyrrolidone. This method is defined at Currenta GmbH & Co. OHG as method no. 2011-0232602-92D, which can be requested there.

[0051] The prepolymer preferably has a number average molecular weight M n in the range from 1500 g / mol to 10 000 g / mol, more preferably 1750 g / mol to 9000 g / mol, particularly preferably 2000 to 7500 g / mol, most preferably 2250 to 7000 g / mol. This number-average molecular weight M n determined by gel permeation chromatography. This number average molecular weight (M n ) and / or all other weight-average molecular weights (M w) of the invention, unless otherwise stated, determined by gel permeation chromatography with degassed tetrahydrofuran (THF) as eluent with a polystyrene as standard (preferably based on 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 for size exclusion chromatography (e.g., PSS SDV 5pm, PSS SDV 1000 Ä, PSS SDV 100 Ä, PSS SDV 50 Ä) connected in series. These columns are selected to ensure sufficient separation of the molecular weights 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 averages 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 analysis unit and measured using 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 by Currenta GmbH & Co. OHG under AM 2011-0623701-09D, which can be requested from Currenta at any time.

[0052] The prepolymer according to the invention preferably has a glass transition temperature T g from

[0053] > 80°C, more preferably from > 80°C to < 145°C, even more preferably from > 85°C to < 140°C, particularly preferably from > 90°C to < 135°C, most particularly preferably from

[0054] > 95 °C to < 130 °C, whereby the glass transition temperature is determined by means of differential scanning calorimetry, preferably according to 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.

[0055] In process step (i), the at least one diol of formula (Ia) can be initially charged. In this case, the at least one diisocyanate of formula (IIa) is subsequently added either completely or over a longer period of time. However, it is also possible for the at least one diol of formula (Ia) and the at least one diisocyanate (IIa) to be fed to the reactor at the same time. Process step (i) is preferably carried out in a temperature range of the heating medium from 110 °C to 265 °C, more preferably from 140 °C to 260 °C, particularly preferably from 170 °C to 255 °C, and most preferably from 200 °C to 250 °C. The reaction is exothermic, so that the reaction can preferably also be counter-cooled.

[0056] Process step (i) can be carried out under nitrogen at atmospheric pressure. However, the process step can also be carried out under reduced or elevated pressure.

[0057] 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.

[0058] Process step (i) can be carried out in the absence or presence of at least one catalyst. Process step (i) is preferably 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 can be used.Particularly preferably, aliphatic 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 aminoalkylureas), in particular (3-dimethylaminopropylamine)urea) and tin catalysts (such as monoalkyltin oxide, dialkyltin oxide, dialkyltin dilaurate, tin octoate) can be used.

[0059] As catalysts, preference is given to using (A) urea, urea derivatives, and / or (B) the above-mentioned amines and amino ethers, characterized in that the amines and amino ethers contain a functional group that reacts chemically with the isocyanate. The functional group is preferably a hydroxyl group or a primary or secondary amino group. These particularly preferred catalysts have the advantage of exhibiting greatly reduced migration and emission behavior. Examples of particularly preferred catalysts are: (3-dimethylaminopropylamine) urea, 1,1'-((3-(dimethylamino)propyl)imino)bis-2-propanol, N-[2-[2-(dimethylamino)ethoxy]ethyl]-N-methyl-1,3-propanediamine and 3-dimethylaminopropylamine and its derivatives and the comparable molecules in which the dimethylamino group is replaced by a pyrrolidine group according to WO 2022 / 112157 A1.

[0060] The use of monobutyltin oxide and / or dibutyltin oxide as catalyst in process step (i) is particularly preferred.

[0061] 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, very particularly preferably 50 to 170 ppm, based on the mass of all diisocyanates used.

[0062] In the context of the present invention, ppb and ppm are to be understood as parts by weight, unless otherwise stated.

[0063] The prepolymer obtained by process step (i) is (essentially) OH-terminated due to the defined ratio of diol to diisocyanate. Furthermore, unreacted aliphatic diol of formula (Ia) (or also of formula (X), if present) is usually still present immediately after completion of process step (i), since an excess of diol was used. This diol(s) may be present in process step (ii) or removed beforehand.

[0064] In one aspect of the process according to the invention, it is characterized in that between process steps (i) and (ii), at least a portion of the unreacted aliphatic diol of formula (Ia) is removed from the prepolymer. If present, the at least one further aliphatic diol, preferably of formula (X), can also be removed.

[0065] The unreacted aliphatic diol of formula (Ia) (and optionally of formula (X) and optionally further components) is preferably removed, for example, by distillation, precipitation, and / or thin-film evaporation. Those skilled in the art are familiar with various processes that can be used to remove the aliphatic diol of formula (Ia).

[0066] 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 a carbonyl source. Depending on whether at least partially unreacted diol of formula (Ia) and optionally of formula (X) is still present in the prepolymer, this can also react with the diaryl carbonate in process step (ii).

[0067] The diaryl carbonate is preferably 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, based on 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, if appropriate, also from unreacted diol and / or further diol. The concentration of the OH groups in the prepolymer is preferably determined by determining the OH number, as described above. However, it can also be calculated theoretically.

[0068] According to the invention, it may be possible that process steps (i) and (ii) cannot be completely separated from one another. For example, it is possible that the diaryl carbonate of process step (ii) and the catalyst used in process step (ii) are already present in process step (i). In this case, it cannot be completely avoided that the reaction intended in process step (ii) already takes place 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 the reaction of OH groups with the diaryl carbonate occur (process step (ii)). The person skilled in the art is able to carry out these intended reactions so that they take place primarily in the aforementioned order.

[0069] Preferably, the prepolymer obtained from process step (i) is not isolated. This means that process step (ii) preferably follows immediately after process step (i). This can be achieved, as already described above, 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). This can also be achieved by adding the diaryl carbonate and / or the catalyst and increasing the temperature and applying a vacuum.

[0070] Process step (ii) is preferably carried out at a heating medium temperature of 210°C to 270°C, more preferably 220°C to 265°C, and most preferably 230°C to 260°C. The specified temperature is preferably the final temperature. According to the invention, the final temperature can be achieved by gradually increasing the temperature. The reaction in process step (ii) generally produces a condensation product. 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 gradually reduced. Most preferably, the vacuum in the last stage is 10 mbar to 0.01 mbar.

[0071] 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. The skilled person is able to select the appropriate catalyst depending on the reactivity of the substances used.

[0072] All inorganic or organic basic compounds, for example lithium, sodium, potassium, caesium, 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, tetraphenylphosphonium fluoride, tetraphenylphosphonium tetraphenylboranate, dimethyldiphenylammonium hydroxide, tetraethylammonium hydroxide, cethyltrimethylammonium tetraphenylboranate, cethyltrimethylammonium phenolate, l,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-triazabicyclo-[4,4,0]-dec-5-ene, 7,7'-decylidenedi-l,5,7-triazabicyclo-[4,4,0]-dec-5-ene, 7,7'-dodecylidenedi-l,5,7-triazabicyclo-[4,4,0]-dec-5-ene or phosphazenes such as Phosphazene base Pl-t-Oct = tert. -Octyl -imino-tris-(di-methylamino)-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.

[0073] Phosphonium catalysts of the formula (VIII) are particularly suitable: where Ra, Rb, Rc and Rd can be the same or different C 1 -C 10 -alkyls, C 1 -C 10 -aryl, C 7 -C 18 -arylalkyls or C 5 -C 12 -cycloalkyls, preferably methyl or C 1 -C 14 -aryls, particularly preferably methyl or phenyl, and X can be an anion such as hydroxide, sulfate, hydrogen sulfate, hydrogen carbonate, carbonate or a halide, preferably chloride or an alkylate or arylate of the formula -OR, where R can be a C 1 -C 14 -aryl, C 7 -C 15 -arylalkyl or C 5 -C 12 -cycloalkyl, preferably phenyl.

[0074] Particularly preferred catalysts are monobutyltin oxide, dibutyltin oxide, lithium hydroxide, lithium acetate dihydrate, sodium acetate trihydrate, 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, zinc acetate, and tetraisopropyl orthotitanate are very particularly preferred. Sodium methylate is also preferred.

[0075] These catalysts can be used in the amount range from 0.1 to 1000 ppm, preferably in the range from 0.5 to 500 ppm and particularly preferably in the range from 1 to 200 ppm, very particularly preferably in the range from 1 to 100 ppm in relation to the total starting materials (diol(s) + diisocyanate(s) + diaryl carbonate).

[0076] The process according to the invention produces thermoplastic poly(urethane-co-carbonate)s that exhibit good optical properties. This is due, among other things, to the fact that the thermoplastic poly(urethane-co-carbonate)s according to the invention are amorphous. In particular, the poly(urethane-co-carbonate)s according to the invention are transparent. The term "transparent" within the meaning of the present invention is preferably understood to mean that injection-molded sheets have a light transmission in the VIS range of the spectrum (380 to 780 nm, transmittance TVIS) of at least 20%, preferably at least 50%, further preferably at least 70%, particularly preferably at least 80%, most preferably at least 88%, determined according to DIN ISO 13468-2:2006 (D65, 10°, layer thickness of the sample sheet: 4 mm).Likewise, these injection-molded sheets preferably have a turbidity of less than 30%, more preferably less than 20%, particularly preferably less than 10%, particularly preferably less than 7%, most preferably less than 3%, as determined according to ASTM D1 003:2013. In particular, this refers to injection-molded sheets that exhibit visual transparency, i.e., they reproduce the background.

[0077] 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. The poly(urethane-co-carbonate) according to the invention offers the advantage that its properties are similar to those of common aromatic polycarbonates. Because the poly(urethane-co-carbonate)s according to the invention are amorphous, they exhibit, in particular, no relevant shrinkage, thus preferably exhibiting a shrinkage of less than 1% in any spatial direction. The term "shrinkage" is known to those skilled in the art in connection with polymers, in particular crystalline polymers. The term preferably refers to the effect that, upon cooling of a polymer melt, the formation of crystals leads to a reduction in volume. As a result, the volume and dimensions of an injection-molded part decrease 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 article. Therefore, aromatic polycarbonates cannot simply be replaced by crystalline polymers in standard plasticizing processes.

[0078] Furthermore, the thermoplastic poly(urethane-co-carbonate)s according to the invention have good mechanical properties, for example at least a tough fracture at room temperature. The thermoplastic poly(urethane-co-carbonate)s according to the invention therefore have, in particular, a good property profile which is comparable, preferably better, than that of classic aromatic polycarbonates (for example based on bisphenol A). In particular, the thermoplastic poly(urethane-co-carbonate)s according to the invention, in addition to the good mechanical properties, also have good chemical resistance (in particular hydrolysis resistance), good transmission, good birefringence and a low yellowing tendency. In a preferred embodiment, the proportion of aromatic groups in the thermoplastic poly(urethane-co-carbonate) according to the invention is limited, in particular very low, particularly preferably equal to 0 wt.-%, so that the common disadvantages of the presence of aromatic groups in the polymer can be reduced, in particular avoided.

[0079] 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 moldings of all kinds. It can also be processed with other thermoplastics and / or polymer additives to form thermoplastic molding compositions, which are then molded into moldings. The moldings and molding compositions made from a thermoplastic composition containing the thermoplastic poly(urethane-co-carbonate) according to the invention are further subject matters of the present invention. The polymer additives are preferably selected from the group consisting of flame retardants, anti-drip agents, flame retardant synergists, smoke inhibitors, lubricants and mold-release agents, nucleating agents, antistatic agents, conductivity additives, stabilizers (e.g.Thermostabilizers, hydrolysis and heat aging stabilizers as well as transesterification inhibitors), flow promoters, phase compatibilizers, dyes and pigments, impact modifiers as well as fillers and reinforcing materials.

[0080] The molded articles made from a thermoplastic composition containing the thermoplastic poly(urethane-co-carbonate) according to the invention 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 produced sheets or films.

[0081] According to the invention, by using both a cycloaliphatic diol or heterocycloaliphatic diol and a cycloaliphatic or heterocycloaliphatic diisocyanate and by using a ratio of all diols used to all diisocyanates used of 1.30:1.0 to 1.01:1.0, particularly preferably 1.27:1.0 to 1.05:1.0, very particularly preferably 1.25:1.0 to 1.10:1.0, a thermoplastic poly(urethane-co-carbonate) with a high glass transition temperature, preferably of >110°C, further preferably >115°C, particularly preferably >120°C, is obtained. It has furthermore been found to be particularly advantageous to at least partially remove the (unreacted) aliphatic diol (of the formula (Ia) and optionally of the formula (X)) still present after process step (i). This allows the glass transition temperature to be influenced and increased even further.This allows for a targeted adjustment of the glass transition temperature. However, this also always depends on the chemical nature of the diols and diisocyanates used. It will be apparent to those skilled in the art how, among other things, the presence or absence of the repeating unit (V) shown later can be influenced. For example, the thermoplastic poly(urethane-co-carbonate) according to the invention generally contains repeating units of formula (V) if previously unreacted diols are still present in the prepolymer at the beginning of process step (ii).

[0082] It has surprisingly been found that a poly(urethane-co-carbonate) with a minimum molecular weight, which has at least one specific structure of the formula (I) and at least one specific structure of the formula (II) and has a defined molar proportion of carbonate groups, based on the sum of the carbonate and urethane groups, and which was preferably prepared by the process according to the invention, has a glass transition temperature preferably of at least 110 °C, more preferably > 115 °C, particularly preferably > 120 °C. Also, comparatively little phenol is formed during preparation. The structure of the formula (I) can be obtained, for example, by using an aliphatic primary diol which has at least one cycle. The structure of the formula (II) can be obtained by using a secondary or tertiary diisocyanate which has at least one cycle.It was found that the glass transition temperature can be specifically adjusted by the proportion of carbonate groups in relation to the urethane groups in the copolymer, in particular a glass transition temperature of at least 110 °C can be achieved.

[0083] It is preferred that the thermoplastic poly(urethane-co-carbonate) has a glass transition temperature of at least 110 °C, more preferably > 110 °C to < 150 °C, particularly preferably > 115 °C to < 145 °C, most preferably > 120 °C to < 140 °C. The glass transition temperature (T g ) are preferably determined by means of 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 T gis determined as the turning point in the second heating process. The thermoplastic poly(urethane-co-carbonate)s according to the invention accordingly exhibit good heat resistance. 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, deep drawing). The ratio of carbonate to urethane groups can be influenced, for example, by the ratio of the diol(s) used to the diisocyanate(s) used. Likewise, different copolymers with different ratios of carbonate to urethane groups can be mixed in a blend in order to specifically adjust a ratio.

[0084] The thermoplastic poly(urethane-co-carbonate) has a proportion of > 1 mol-% to < 15 mol-%, preferably > 3 mol-% to < 14 mol-%, more preferably > 5 mol-% to < 13 mol-%, based on the sum of the carbonate and urethane groups in the poly(urethane-co-carbonate), carbonate groups, wherein the mol-percentages of carbonate and urethane groups are 13C NMR spectroscopy. The skilled person is able to determine the proportion of carbonate groups as well as the proportion of urethane groups 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 more 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 of the urethane group is usually in the range of 156 ppm. The carbon atom of the carbonate group can usually be found at a chemical shift of 155.5 ppm (see Experimental Section).To determine the mol% carbon atom ratio, the area under the peaks is integrated and then plotted against each other. This is a method well known to those skilled in the art.

[0085] It has surprisingly been found that the defined proportion of carbonate groups makes it possible to obtain polymers which have a glass transition temperature of at least 110 °C.

[0086] The thermoplastic poly(urethane-co-carbonate) also has a weight-average molar mass of at least 40,000 g / mol. The poly(urethane-co-carbonate) according to the invention preferably has a weight-average molar mass of 40,000 g / mol to 190,000 g / mol, particularly preferably of 45,000 g / mol to 160,000 g / mol, and very particularly preferably of 50,000 g / mol to 130,000 g / mol. The molar mass is preferably determined as described above. It has been found that the poly(urethane-co-carbonate) according to the invention has good properties, in particular good thermoplasticity, in this defined molar mass range. Likewise, the mechanical properties, in particular toughness at least at room temperature, are good in this molar mass range.It was also found that if aromatic groups are present in the poly(urethane-co-carbonate) according to the invention, lower molecular weights may be present and still good mechanical properties, in particular ductility, may be present.

[0087] A glass transition temperature and a molecular weight within the aforementioned ranges enable the thermoplastic poly(urethane-co-carbonates) according to the invention to be used in common plasticizing processes (e.g. injection molding, (co)extrusion, blow molding, deep drawing), in particular so that they have "thermoplastic" properties known to those skilled in the art. According to the invention, the term "thermoplastic" is preferably understood to mean a polymer which can be deformed in a temperature range, in particular above room temperature, more preferably above 50°C, most preferably above 90°C. This deformation is preferably reversible. In particular, the term "thermoplastic" preferably serves to differentiate between thermoset and / or elastomeric polymers.Such thermoset and / or elastomeric polymers exhibit physical cross-linking of the individual polymer chains, which makes deformation beyond the elastic range irreversible. Such polymers cannot be deformed / shaped using conventional plasticizing processes.

[0088] The thermoplastic poly(urethane-co-carbonate) according to the invention has both urethane and carbonate groups. It is not excluded that the poly(urethane-co-carbonate) according to the invention also has further functional groups (in particular also those that differ from the structures of formulas (I) and (II)). However, it is preferred that the poly(urethane-co-carbonate) according to the invention does not have any ether groups and / or ester groups. Thus, the poly(urethane-co-carbonate) according to the invention preferably has no ether groups. Particularly preferably, the poly(urethane-co-carbonate) according to the invention does not have any linear ether groups. This preferably means that the poly(urethane-co-carbonate) according to the invention does not comprise any polyethylene oxide and / or polypropylene oxide segments. Likewise preferably, and particularly preferably at the same time, the poly(urethane-co-carbonate) according to the invention has no ester groups.The absence of such groups is preferred according to the invention, since according to the invention, preferably no polyether polyols and / or polyester polyols are used in the preparation of the poly(urethane-co-carbonate) according to the invention. It is understood that the components used may contain conventional impurities, which arise, for example, from their preparation processes. Thus, the poly(urethane-co-carbonate) according to the invention 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.

[0089] It is preferred that no structures are included that arise when a structure of formula (II) is directly bonded to a structure of formula (II). This would result in the formation of urea groups.

[0090] It is apparent to the person skilled in the art that further functional groups can be incorporated into the poly(urethane-co-carbonate) according to the invention by means of special monofunctional chain terminators.

[0091] However, the poly(urethane-co-carbonate) according to the invention particularly preferably comprises essentially urethane and carbonate groups for linking the formulas (I) and (II) to one another. These structures thus formed form the essential part of the polymer chain of the poly(urethane-co-carbonate). For example, by linking at least some of the structures (I) directly to one another with at least one other structure of the formula (I), a structure of the formula (IA) can be formed:

[0092] R 1for the meanings given with respect to formula (I), including all preferred versions. It will be apparent to the person skilled in the art that a carbonate group is formed by the direct linkage of at least some of the structures (I) with at least one other structure of formula (I).

[0093] Likewise, by linking at least some of the structures of formula (I) and (II) directly to each other, a structure of formula (IIA) can be formed:

[0094] R 1 and R 2 for the meanings given with respect to formula (I) or (II), including all preferred versions. It will be apparent to the person skilled in the art that the direct linkage of at least some of the structures of formula (I) with (II) forms a urethane group.

[0095] The structures of formulas (IA) and (IIA) are preferably randomly distributed in the poly(urethane-co-carbonate) according to the invention. This applies in particular if further structures are present that differ from the structures of formulas (I) and (II) / (IA) and (IIA).

[0096] The poly(urethane-co-carbonate) according to the invention is preferably obtained by the process according to the invention explained in more detail above. In this process, diols are first reacted with diisocyanates. The resulting prepolymer is then reacted with a carbonyl source. Such a process essentially produces urethane and carbonate groups. It will be 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, the urethane and carbonate groups continue to be the groups that form the essential part of the functional groups in the polymer chain of the poly(urethane-co-carbonate).This particularly preferably means that the functional groups of the poly(urethane-co-carbonate) consist of at least 80 mol%, particularly preferably at least 90 mol%, of the functional groups “urethane” and “carbonate”, wherein the mol% preferably refers to all functional groups which have heteroatoms.

[0097] According to the invention, the poly(urethane-co-carbonate) comprises structures of the formulas (I) and (II). This does not exclude the presence of other structures, in particular between the urethane groups and / or carbonate groups in the poly(urethane-co-carbonate) according to the invention. These could, for example, be introduced through the use of further diols and / or further diisocyanates. However, it is preferred that the poly(urethane-co-carbonate) according to the invention consists essentially of the structures of the formulas (I) and (II). The person skilled in the art will appreciate the relationship between structures (I) and (II), 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% by weight, preferably at least 75% by weight, more preferably at least 80% by weight, very preferably at least 90% by weight, and especially preferably at least 95% by weight.-% consists of the structures of formulas (I) and (II). Here, too, the skilled person will appreciate the relationship between structures (I) and (II), in particular that structures (IA) and (IIA) are included.

[0098] According to the invention, the poly(urethane-co-carbonate) comprises structures of the formula (I)

[0099] (I), where each R 1 in the formula (I) each independently represents an aliphatic group having 4 to 18 carbon atoms, which has at least one cycle and this cycle may optionally contain at least one heteroatom, preferably oxygen, and wherein the wavy lines in formula (I) each represent the connection of the structure of formula (I) into the chain of the poly(urethane-co-carbonate). It is evident that when R 1 has more than one cycle, one or more of the 4 to 18 carbon atoms can also be part of two cycles. Preferably, the R1 in formula (I), (IA), (IIA), but also in the formulas (IV) (IVi), (V) and (VI) shown later represented by formula (1) or formula (2), where the positions marked with the star symbol in formulas (1) and (2) are the positions at which the CH2 groups shown in formulas (I), (IA), (IIA), and the formulas (IV), (IVi), (V) and (VI) shown later are located, respectively.

[0100] Most preferably, formula (I) is represented by the following formulas (II) or (12): where the wavy lines in formulas (II) and (12) each represent the linkage of the structure of formulas (II) and (12) into the chain of the poly(urethane-co-carbonate). Formula (II) is most preferably based on 1,4-cyclohexanediomethanol.

[0101] The poly(urethane-co-carbonate) according to the invention may, in addition to the structures of formula (I), also comprise at least one further structure of formula (Ii): where each R 6in formula (Ii) 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 6has at least one cycle, is not bound into structure (Ii) via a CH2 group at least on one side, preferably on both sides, and wherein the wavy lines in formula (Ii) each represent the connection of the structure of formula (Ii) into the chain of the poly(urethane-co-carbonate). These structures of formula (Ii) can be at least partially directly bonded to another structure of formula (Ii) to form a carbonate group, or else at least partially to a structure of formula (I). Likewise, the structures of formula (Ii) can be at least partially bonded to a structure of formula (II) to form a urethane group, or else at least partially to a structure of formula (IIi) defined later. The structure of formula (Ii) is preferably present in a statistically distributed manner in the poly(urethane-co-carbonate) according to the invention.Most preferably, the poly(urethane-co-carbonate) according to the invention does not comprise a structure of formula (li).

[0102] However, if a structure of formula (li) is also present, it is particularly preferably at least one further structure of formula (lia) to (lid) where the wavy lines in formulas (1a) to (1d) each represent the connection of the structure of the formulas into the chain of the poly(urethane-co-carbonate). The amount of the further structure of the formula (1i) or of the particularly preferred structures (1a) to (1d) in the poly(urethane-co-carbonate according to the invention), if such a structure is present, is preferably chosen such that the resulting glass transition temperature of the poly(urethane-co-carbonate) remains above 110°C. In addition, ductile fracture should be present at least at room temperature. The poly(urethane-co-carbonate) according to the invention particularly preferably contains at most 75 mol%, particularly preferably at most 60 mol%, likewise preferably at most 40 mol%, likewise particularly preferably at most 25 mol%, likewise preferably at most 10 mol% and very particularly preferably at most 5 mol% of the further structure of the formula (1i) orof the preferred structures (lia) to (lid) in relation to the sum of the structures (li) (or (lia) to (lid)) and the structures (I). It is apparent to the person skilled in the art that the expression “at most” can include 0 mol%, since these are optional further structures of the formula (li). Most preferably, none, thus 0 mol%, of the further structure of the formula (li) is present. However, if at least one structure of the formula (li) or one preferred structure of the formula (lia) to (lid) is present, the expression “at most” in this context means that more than 0 mol% is present.

[0103] However, the poly(urethane-co-carbonate) according to the invention preferably does not contain any structures of the formula (li) in which R 6 represents a -CH2CH2CH2CH2- group.

[0104] According to the invention, the poly(urethane-co-carbonate) further comprises structures of the formula (II) where each R 2in formula (II) each independently represents a bridging aliphatic structure having 6 to 18 carbon atoms, wherein said bridging structure has at least one cycle and said cycle may optionally contain at least one heteroatom, and wherein the bridging structure is linked to the nitrogen atoms shown in structure (II) via a secondary or tertiary carbon atom, and wherein the wavy lines in formula (II) each represent the linkage of the structures of formula (II) into the chain of the poly(urethane-co-carbonate). It is understood that the at least one secondary or tertiary carbon atom, or both secondary or tertiary carbon atoms, which are each linked to the nitrogen atoms shown in the structure of formula (II), may be part of the at least one cycle or of different cycles. The terms “secondary” and “tertiary carbon atom” are also known to the person skilled in the art.Preferably, this means that a secondary carbon atom is bonded to two further carbon atoms (and the other two substituents are freely selectable, but are not carbon) and that a tertiary carbon atom is bonded to three further carbon atoms (and the other substituent is freely selectable, but is not carbon). Applied to formula (II) of the present invention, this means that a secondary carbon atom is bonded to two further carbon atoms and the nitrogen atom, with the last substituent being freely selectable (but is not carbon). Likewise, with respect to formula (II) of the present invention, this means that a tertiary carbon atom is bonded to three further carbon atoms and the nitrogen atom.

[0105] Preferably R 2 for a Ce to Cis-cycloalkylene group according to the preferred definition given above, taking into account the limitation as to R2 specified.

[0106] Particularly preferred is the structure R 2 in formula (II), (IIA) or the formulas (IV), (IVi), (V) or (VI) shown later, represented by one of the formulas (3) to (8), wherein the positions marked with the star “*” in formulas (3) to (8) are the positions at which the nitrogen atoms shown in formula (II), (IIA), the formulas (IV), (IVi), (V) and (VI) shown later are located, respectively, and wherein 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 wherein each R 3 in formula (5) independently represents a methyl or ethyl group and p represents 0, 1, or 2.

[0107] R is particularly preferred 2represented 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-linked structures is preferred. Furthermore, a mixture is preferred in which at least 80 mol% of the structures have 4,4-linkages and the remainder are 2,4- or 2,2-linkages.

[0108] The poly(urethane-co-carbonate) according to the invention can, in addition to the structures of formula (II), also comprise at least one further structure of formula (IIi): where each R 7 in the formula (Ili) for

[0109] - a linear alkylene group with 4 to 12 carbon atoms,

[0110] - a cycloaliphatic group having 5 to 20, preferably 7 to 18 carbon atoms, but the bonding of the structure R 7to at least one of the nitrogen atoms shown in structure (Ili) via a primary carbon atom, or

[0111] - an aromatic group having 6 to 18 carbon atoms, and wherein the wavy lines in formula (Ili) each represent the connection of the structure of formula (Ili) into the chain of the poly(urethane-co-carbonate). These structures of formula (Ili) can be at least partially bonded to a structure of formula (I) to form a urethane group, or at least partially bonded to a structure of formula (Ii). Preferably, the structure of formula (Ili) is randomly distributed in the poly(urethane-co-carbonate) according to the invention. Very particularly preferably, the poly(urethane-co-carbonate) according to the invention does not comprise a structure of formula (Ili).

[0112] However, if a structure of formula (Ili) is present, the poly(urethane-co-carbonate) according to the invention preferably comprises, in addition to the structures of formula (II), at least one further structure of formula (Ilia) to (Ilih): where each R 18 in the formula (Ilib) independently represents hydrogen or a methyl group and f in formula (Ilib) represents a number between 1 and 6, each R 3 in the formula (Ilid) independently represents a methyl or ethyl group and p represents 0, 1, or 2, each R 3 in the formula (IIIe) independently represents a methyl or ethyl group and p represents 0, 1, or 2 and d each independently represents 0 or 1, wherein each R 3in formula (Ilig) independently of one another represents a methyl or ethyl group, p represents 0, 1, or 2, and q represents 0 or 1, and wherein the positions marked with the star symbol in formulas (Ilia) to (Ilih) are the positions at which the nitrogen atoms shown in formula (Ili) are located. The amount of the further structure of formula (Ili) or of the preferred structures (Ilia) to (Ilih) in the poly(urethane-co-carbonate) according to the invention is preferably selected such that the resulting glass transition temperature of the poly(urethane-co-carbonate) remains > 110 °C, more preferably > 115 °C, particularly preferably > 120 °C. In addition, ductile fracture should be present at least at room temperature. In addition, the amount of the further structure of formula (Ili) must, if necessary, be adjusted so that the preferred aromatic proportion of the resulting poly(urethane-co-carbonate), as preferably defined according to the invention, is maintained.The poly(urethane co-carbonate) according to the invention particularly preferably contains at most 75 mol%, especially preferably at most 60 mol%, likewise preferably at most 40 mol%, likewise particularly preferably at most 25 mol%, likewise preferably at most 10 mol% and very particularly preferably at most 5 mol% of the further structure of the formula (Ili) or of the preferred structures (Ilia) to (Ilih) in relation to the sum of the structures (Ili) (or (Ilia) to (Ilih)) and the structures (II). It is apparent to the person skilled in the art that the expression “at most” can encompass 0 mol%, since these are optional further structures of the formula (Ili). However, if at least one structure of the formula (Ili) or of a preferred structure of the formula (Ilia) to (Ilih) is necessarily present, the expression “at most” in this context means that more than 0 mol% is present.

[0113] Particularly preferably, the poly(urethane-co-carbonate) according to the invention comprises structures of the formula (II), in particular with 1,4-linkage, and / or (12) and structures of the formula (II), in which R 2 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-linked structures is preferred. Furthermore, a mixture is preferred in which at least 80 mol% of the structures have 4,4-linkages and the remainder are 2,4- or 2,2-linkages.

[0114] It is preferred that the thermoplastic poly(urethane-co-carbonate) according to the invention has 0 mol% to <39 mol%, more preferably 0 mol% to <37 mol%, even more preferably 0 mol% to 35 mol%, particularly preferably 0 mol% to 33 mol%, very particularly preferably 0 mol% to 5 mol%, extremely preferably 0 mol% of aromatic groups. It is clear that the formulation “at most” covers the range from 0 mol% to the stated mol%. The thermoplastic poly(urethane-co-carbonate) according to the invention is very particularly preferably aliphatic. However, as already explained above, this does not exclude traces of aromatic compounds which are present in the polymer as impurities and / or end groups. The aromatic fraction of a thermoplastic poly(urethane-co-carbonate) can be calculated from the stoichiometry of the starting materials. Aromaticity is preferably determined by 'H-NMR spectroscopy.The skilled person is able to determine the proportion of polyurethane composed of one or more aromatic diisocyanates, as well as the proportion of polycarbonate, using this method. For example, the polymer can be dissolved in CDCl3. Should an insoluble residue be obtained, dimethyl sulfoxide-d6 can also be used as a solvent. Tetramethylsilane is more 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 or polycarbonate. From the proportion of polyurethane, the aromaticity can be determined using the molecular weight of the repeating unit of the polyurethane and the proportion of aromatic hydrocarbons contained therein. This is a method known to the skilled person and is preferred for determining the proportion of aromatic groups.

[0115] It is preferred that the thermoplastic poly(urethane-co-carbonate) according to the invention comprises the structural formula (IV) where each R 1 has the meanings given for formula (I), where the group -CH2-R'-CH2- enclosed by the round brackets also partly independently of one another represents R 6 provided that at least part of the structures is -CH2-R'-CH2-, and R 6 represents an aliphatic alkylene group having 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, wherein R 6 , if R 6 has at least one cycle, is not bound into the structure (IV) via a CH2 group at least on one side, preferably on both sides, and each R 2 has the meanings given for formula (II), and the expression R 2 / R 7means that the group R 2 at least partly also independently of each other for R 7 provided that at least some of the groups R 2 is, and R 7 has the meanings given for formula (IIi), m is the arithmetic mean of the repeating units and is a number > 4.0, preferably

[0116] > 4.5, particularly preferably > 4.75, most preferably > 5.0 and the wavy lines represent the connection of the structure of formula (IV) into the chain of the poly(urethane-co-carbonate). The arithmetic mean of the repeat units m is preferably a number

[0117] < 25.0, particularly preferably < 21.0, most preferably < 10.0.

[0118] It is also preferred, in particular at the same time it is preferred that in formula (IV) the larger proportion of the sum of the groups R 2 and R 7 Group R 2This means that the majority of groups are bonded into the polymer chain via two secondary and / or tertiary carbon atoms.

[0119] It will be clear to the person skilled in the art how the structure of formula (IV) results from the structures of formula (I), (II), (Ii) and / or (Ii). Formula (IV) is particularly preferably represented by the following formula (IVi) where each R 1 , R 2 and m has the meanings given for formula (IV). The skilled person will be aware that formula (IVi) may also be randomly interrupted by the presence of formulas (li) and / or (IIi). However, the polymer most preferably does not contain any groups R 6 and R 7 on.

[0120] Furthermore, it is preferred that the thermoplastic poly(urethane-co-carbonate) according to the invention comprises, in addition to the structure of formula (IV) or (IVi), 0 to 10 wt.%, preferably 0.2 to 5 wt.%, of repeating units of formula (V) where each R 1 has the meanings given for formula (I), where the group enclosed by the round brackets -CFF-R'-CFb- also partly independently of one another represents R 6 can stand, and R 6 has the meanings given for formula (li), n is the arithmetic mean of the repeating units, and the wavy lines represent the connection of the structure of formula (IV) into the chain of the poly(urethane-co-carbonate). The arithmetic mean n is a number that arises statistically. The skilled person is able to determine the proportion of groups of formula (IV) using methods commonly used, such as NMR spectroscopy. The method may also depend on the type of monomers used.

[0121] Most preferably, the thermoplastic poly(urethane-co-carbonate) according to the invention has a structure of the formula (VI)

[0122] (VI) where each R 1 has the meanings given for formula (I), where the group enclosed by the round brackets -CFL-R'-CFL- also partly independently of one another represents R 6 provided that at least part of the structures is -CFL-R'-CFL-, and R 6 has the meanings given for formula (li), and each R 2 has the meanings given for formula (II), and the expression R 2 / R 7 means that the group R 2 at least partly also independently of each other for R 7 provided that at least some of the groups R 2 is, and R 7has the meanings given for formula (IIi), m and r are each the arithmetic mean of the respective repeating units, where m is a number between > 4.0, preferably > 4.5, particularly preferably > 4.75, very particularly preferably > 5.0 and x or 1-x is the relative ratio of the respective repeating units to one another. The arithmetic mean of the repeating units m is preferably a number

[0123] < 25.0, particularly preferably < 21.0, most preferably < 10.0. However, the polymer most preferably has no groups R 6 and R 7 on.

[0124] It is preferred that r be at least 1. Those skilled in the art are able to correlate r with the molecular weight. It is evident that when r is 1, formula (VI) is a repeating unit of the poly(urethane-co-carbonate) according to the invention. This unit can be randomly distributed in the poly(urethane-co-carbonate) according to the invention. It can also be bonded, inter alia, to another repeating unit of formula (VI). This then makes r greater than 1.

[0125] It is obvious to a person skilled in the art that x must be less than 1. It is obvious to a person skilled in the art that x must be < 1. If unreacted diol, in particular of formula (Ia) and optionally of formula (X), is present, x is less than 1.

[0126] It is obvious to the person skilled in the art that the end groups in formula (VI) do not necessarily have to be methyl groups, but can merely represent a potential end of the chain of formula (VI) or can be a further point of attachment to other groups.

[0127] The skilled person is able to see the connection between the process according to the invention and the thermoplastic poly(urethane-co-carbonate) according to the invention. In particular, the skilled person can see the connection between formulas (Ia) and (IIa) and formulas (I), (II), (III), (IIIa), (IV), (IVi), (V), and (VI).

[0128] The process according to the invention is preferably characterized in that the process produces the thermoplastic poly(urethane-co-carbonate) according to the invention in all embodiments, preferences, and combinations of preferences. In a further aspect of the present invention, a thermoplastic poly(urethane-co-carbonate) is provided which is obtained by the process according to the invention in all embodiments, preferences, and combinations of preferences. This is preferably the thermoplastic poly(urethane-co-carbonate) according to the invention.

[0129] Figures:

[0130] Figure 1: GPC spectrum of a prepolymer (Example 4) based on TCD-DM and H12-MDI in the used molar ratio of 1.25:1 (DiokDiisocyanate), plotted against the molar mass.

[0131] Figure 2: Illustration of the subdivision of the GPC spectrum of a prepolymer (Example 4) for determining the arithmetic mean of the repeating unit "m" of the prepolymer and, if applicable, the residual diol content. The designations A to J represent individual peaks that must therefore be considered separately. Figure 3: GPC spectrum of a prepolymer (Example 3) based on TCD-DM and H12-MDI in a molar ratio of 1.1:1 (diol:diisocyanate), plotted against the molar mass.

[0132] Figure 4: Illustration of the subdivision of the GPC spectrum of a prepolymer (Example 3) for determining the arithmetic mean of the repeating unit "m" of the prepolymer and, if applicable, the residual diol content. The designations A to K represent individual peaks that must therefore be considered separately.

[0133] Figure 5: 13C-NMR spectrum of a poly(urethane-co-carbonate) (Example 8) based on TCD-DM and H12-MDI in the molar ratio of 1.25:1 (diisocyanate).

[0134] Examples

[0135] Materials used:

[0136] Diol component (according to formula (1a) according to the invention)

[0137] CHDM (la, 1) 1,4-cyclohexanedimethanol: Mixture of cA-l,4-cyclohexanedimethanol and trara- 1,4-cyclohexanedimethanol, CAS: 105-08-8, 99%, Sigma-Aldrich, Germany, was used without further purification

[0138] TCD-DM (la, 2) Tricyclodecanedimethanol: mixture of isomers, CAS: 26896-48-0, 96%, Sigma-Aldrich, Germany, was used without further purification

[0139] Diisocyanate component (according to the invention according to formula (Ila))

[0140] H12-MDI (Ila, 7) Dicyclohexylmethane-4,4'-diisocyanate (Dicyclohexylmethane-2,4'-diisocyanate (< 10 wt%) and Dicyclohexylmethane-2,2'-diisocyanate (< 2 wt%): mixture of cis- and tra-isomers), CAS: 5124-30-1 (based on 4,4'-linkage), Covestro AG, Germany, was used without further purification

[0141] Carbonyl source (for use of the urethanediol prepolymer for PUC production)

[0142] DPC Diphenyl Carbonate, CAS: 102-09-0, Covestro AG, Germany, was freshly distilled before use

[0143] Catalyst (for use of the urethanediol prepolymer for PUC production) Kat Monobutyltin oxide, CAS: 2273-43-0, TIB Chemicals AG, Germany, was used without further purification

[0144] Analytical methods:

[0145] GPC:

[0146] The molecular weight 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 gentle 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 Å, PSS SDV 100 Å, PSS SDV 50 Å). Calibration was 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) and was adapted to the 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 under AM 2011-0623701-09D, which can be requested from Currenta at any time.

[0147] Determination of the arithmetic mean of the repeating unit m in prepolymers using Example 4

[0148] During prepolymer synthesis, the diol component was always used in excess of the diisocyanate component. This resulted in the formation of oligomers with an arithmetic mean repeating unit of m (see, for example, formula (III) or (IIIa)), 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 4 in Figure 1).

[0149] It is clear to the person 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 one another in the GPC spectrum due to the low resolution.

[0150] In these cases, a clear assignment of the oligomers using GPC is not possible, so the arithmetic mean of the repeating unit m can only be determined approximately as a minimum value (represented by a ">"). The following illustrates the approximate determination of this arithmetic mean of the repeating unit m and the residual diol amount using Example 4.

[0151] Both the m of the prepolymers and the remaining unreacted diol in wt. % were determined from the GPC spectra plotted against the elution volume (Figure 1). Each detected peak, if unambiguous, was assigned to either the unreacted monomer-diol or the oligomers based on the molecular weight. If the peaks were not clearly separated, which was often the case with longer-chain oligomers, the division was preferentially made at the nadir between two peaks until no more nadir was measured (as seen in the GPC spectrum of Example 4 in Figure 2).

[0152] The GPC spectrum in Figure 2 for Example 4 resulted in the following areas F (in %):

[0153] A: Prepolymer with repeating unit m = 6 (F = 58.6%) (here it is clear that oligomers with a higher repeating unit are also included, but the value is still artificially referred to as “6”)

[0154] B: Prepolymer with repeating unit m = 5 (F = 8.9%)

[0155] C: Prepolymer with repeating unit m = 4 (F = 8.6%)

[0156] D: Prepolymer with repeating unit m = 3 (F = 8.4%)

[0157] E: Prepolymer with repeating unit m = 2 (F = 7.6%)

[0158] F: Prepolymer with repeating unit m = 1 (F = 5.7%)

[0159] G: unknown (F = 0.1%)

[0160] H: unknown (F = 0.2%)

[0161] I: unknown (F = 0.1%)

[0162] J: residual diol TCD-DM (F = 1.8%)

[0163] According to the weighted arithmetic mean, m was determined.

[0164] 1 x F(m = 1) + 2 x F(m = 2) + — I- nx F(m = ri) m =

[0165] F Prepolymer) With F(Prepolymer) = 97.8%

[0166] 1 x 5.7 + 2 x 7.6 + 3 x 8.4 + 4 x 8.6 + 5 x 8.9 + 6 x 58.6 m = - - = 4.9

[0167] 97.8

[0168] The arithmetic mean of the repeating unit “m” for Example 4 is at least 4.9.

[0169] It is also clear to the person skilled in the art that with a very small excess (< 25 mol%) of diol component, m increases and the proportion of unreacted monomer diol decreases. However, this also leads to poorly resolved GPC spectra, which complicates the precise determination of m by GPC, as shown in Example 3 (see Figures 3 and 4).

[0170] DSC:

[0171] The glass transition temperature (T g ) was determined as the inflection point in the second heating process using differential scanning calorimetry (DSC) according to DIN EN ISO 11357-1:2022-02 and DIN EN ISO 11357-2:2020-08, measured at a heating rate of 20 K / min under nitrogen.

[0172] 13 C NMR spectroscopy:

[0173] The ratio of urethane to carbonate groups in the poly(urethane-co-carbonate)s was determined by 13C NMR spectroscopy. Approximately 20 mg of sample was dissolved in a suitable solvent (chloroform-dl) and measured on a Bruker AV III HD 600 NMR spectrometer at a measurement frequency of 151 MHz.

[0174] Measurement parameters:

[0175] Pulse program pulprog zgig30

[0176] Scan per increment NS: 512

[0177] Relaxation time between two scans Dl: 4 see

[0178] The following illustrates the evaluation of the urethane to carbonate group ratio using Example 8 of a poly(urethane-co-carbonate) made from tricyclodecanedimethanol (TCD-DM) and HI 2-MDI in a molar ratio of 1.25:1 (diisocyanate). Reference is made to Figure 5.

[0179] Assignment for the determination of urethane to carbonate from the 13 C NMR spectrum

[0180] Urethane signal at 156 ppm Carbonate signal at 155.6 ppm

[0181] The molar ratio results directly from the areas of the respective signals normalized to 100.

[0182] From the 13 C-NMR spectrum in Figure 5 gives the following estimated molar ratio:

[0183] Urethane = 88

[0184] Carbonate = 12

[0185] Hydroxyl number:

[0186] The hydroxyl number (also called OH number) was determined titrimetrically by Currenta GmbH & Co. OHG in accordance with DIN EN ISO 4629-2. "In accordance" means that pyridine was used instead of the base α'-methyl-2-pyrrolidone used in DIN EN ISO 4629-2. The method used is defined under No. 2011-0232602-92D by Currenta GmbH & Co. OHG, which can be requested from Currenta at any time.

[0187] NCO value:

[0188] The NCO content was determined titrimetrically according to DIN EN ISO 11909:2007-05.

[0189] Production of urethane diol prepolymers (UDO)

[0190] Example 1: Reaction of CHDM (according to formula (Ia, 1)) as diol component with H12-MDI (according to formula (Ila, 3)) as diisocyanate building block in a molar ratio of 1.1:1 (diol.diisocyanate).

[0191] 78.0 g (541 mmol) of CHDM were placed in a flask fitted with a reflux condenser and a dropping funnel. The apparatus was then purged of air and water by alternately evacuating and introducing nitrogen. The mixture was melted at 180 °C under nitrogen blanketing and at atmospheric pressure and stirred for 30 minutes. 129 g (492 mmol) of H12-MDI were added via the dropping funnel within a few seconds. After 10 minutes, the temperature was increased to 200 °C, and the mixture was stirred for 30 minutes at 200 °C. The bath temperature was then increased to 220 °C, and the mixture was stirred for a further 30 minutes at 220 °C before the reaction was stopped. A yellowish, transparent prepolymer with an OH number of 25.1 mg KOH / g and a glass transition temperature of T was obtained. g of 106 °C and a molecular weight M nof 5780 g / mol. Example 2: Reaction of CHDM (according to formula (Ia, 1)) as the diol component with H12-MDI (according to formula (Ila, 3)) as the diisocyanate building block in a molar ratio of 1.25:1 (diol:diisocyanate).

[0192] 103.0 g (714 mmol) of CHDM were placed in a flask fitted with a reflux condenser and a dropping funnel. The apparatus was then purged of air and water by alternately evacuating and introducing nitrogen. The mixture was melted at 160 °C under a nitrogen blanket and at atmospheric pressure and stirred for 30 minutes. 150.0 g (572 mmol) of H12-MDI were added via the dropping funnel within a few seconds. After 20 minutes, the temperature was increased to 180 °C, and the mixture was stirred for 30 minutes at 180 °C. After 30 minutes, a sample was taken for NCO measurement in a nitrogen countercurrent. The NCO value was 0%, and the reaction was stopped. A colorless, transparent prepolymer with an OH number of 62.8 mg KOH / g and a glass transition temperature of T was obtained. g of 97 °C and a molecular weight M n of 2790 g / mol.

[0193] Example 3: Reaction of TCD-DM (according to formula (Ia, 2)) as diol component with H12-MDI (according to formula (Ila, 3)) as diisocyanate building block in a molar ratio of 1.1:1 (diol.diisocyanate).

[0194] 107 g (545 mmol) of TCD-DM were placed in a flask fitted with a reflux condenser and a dropping funnel. The apparatus was then purged of air and water by alternately evacuating and introducing nitrogen. The mixture was melted at 200 °C under a nitrogen blanket and at atmospheric pressure and stirred for 30 minutes. 130 g (496 mmol) of H12-MDI were added via the dropping funnel within a few seconds. The mixture was stirred for 30 minutes at 200 °C. The bath temperature was then increased to 220 °C, and the mixture was stirred for a further 30 minutes at 220 °C before the reaction was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 21.9 mg KOH / g and a glass transition temperature of T gof 128 °C and a molecular weight M n of 4810 g / mol.

[0195] Example 4: Reaction of TCD-DM (according to formula (Ia, 2)) as diol component with H12-MDI (according to formula (Ila, 3)) as diisocyanate building block in a molar ratio of 1.25:1 (diol:diisocyanate).

[0196] 112.2 g (572 mmol) of TCD-DM were placed in a flask fitted with a reflux condenser and a dropping funnel. The apparatus was then purged of air and water by alternately evacuating and introducing nitrogen. The mixture was melted at 200 °C under nitrogen blanketing and atmospheric pressure and stirred for 30 minutes. 100.0 g (381 mmol) of H12-MDI was added via the dropping funnel within a few seconds. The mixture was stirred at 200 °C for 60 minutes. After 60 minutes, the reaction was terminated. A yellowish, transparent prepolymer with an OH number of 54.5 mg KOH / g and a glass transition temperature of T was obtained. gof 104 °C and a molecular weight M n of 2300 g / mol.

[0197] Table 1: Comparison of the results of examples 1 to 4. nb: not exactly determinable, but at least greater than 5

[0198] Production of poly(urethane-co-carbonate)s (PUC) by polycondensation of previously prepared urethanediol prepolymers (UDO) with diphenyl carbonate (DPC)

[0199] Example 5: Reaction of Example 1 as UDO component with DPC as carbonyl source in a molar ratio of 1:1.089 (UDO: DPC) in the presence of cat.

[0200] 110.0 g (24.6 mmol, determined from the measured OH number) of the product from Example 1 and 5.74 g (26.8 mmol) of DPC as well as 0.005 g (43 ppm based on the starting materials product from Example 1 and DPC) of catalyst were placed in a flask fitted with a Vigreux column and distillation bridge. The apparatus was then freed of traces of air and water by alternately evacuating and introducing nitrogen. The mixture was melted at 230 °C under a nitrogen blanket and at atmospheric pressure and stirred for 20 minutes. The temperature was then increased to 240 °C and the pressure reduced to 100 mbar over a period of 20 minutes. Phenol was continuously removed. The mixture was stirred at 100 mbar for approximately 10 minutes. The pressure was then reduced to < 1 mbar over a period of 30 minutes, and the mixture was stirred for a further 60 minutes. The reaction was then stopped. A light yellow, transparent polymer with a M wof 89,200 g / mol, a glass transition temperature T g of 130 °C and a molar carbonate to urethane ratio of 6:94. 4.2 g of distillate, consisting predominantly of phenol, was obtained (corresponding to 3.6 wt.%, based on the starting materials product from Example 1 and DPC).

[0201] Example 6: Reaction of Example 2 as UDO component with DPC as carbonyl source in a molar ratio of 1:1.030 (UDO: DPC) in the presence of cat.

[0202] 100.0 g (56.0 mmol, determined from the measured OH number) of the product from Example 2 and 12.36 g (57.7 mmol) of DPC, as well as 0.005 g (44 ppm based on the starting materials of product from Example 2 and DPC) of catalyst were placed in a flask equipped 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 at atmospheric pressure at 190 °C and stirred for 20 minutes. The pressure was then reduced to 100 mbar over a period of 20 minutes. The mixture was stirred for 10 minutes at 190 °C, for 5 minutes at 200 °C, for 5 minutes at 210 °C, for 5 minutes at 220 °C, for 20 minutes at 230 °C, and for 5 minutes at 240 °C. Phenol was continuously removed. The pressure was then reduced to < 1 mbar over 25 minutes, and the mixture was stirred for another 60 minutes.The reaction was then stopped. A light yellow, transparent polymer with an M was obtained. w of 124,700 g / mol, a glass transition temperature T g of 121 °C and a molar carbonate to urethane ratio of 10:90. 10.9 g of distillate, consisting predominantly of phenol, was obtained (corresponding to 9.7 wt.%, based on the starting materials, product from Example 2 and DPC).

[0203] Example 7: Reaction of Example 3 as UDO component with DPC as carbonyl source in a molar ratio of 1:1.098 (UDO: DPC) in the presence of cat.

[0204] 110.0 g (21.5 mmol, determined from the measured OH number) of the product from Example 3 and 5.05 g (23.6 mmol) of DPC as well as 0.005 g (43 ppm based on the starting materials product from Example 3 and DPC) of Kat were placed in a flask fitted with a Vigreux column and distillation bridge. The apparatus was then freed of traces of air and water by alternately evacuating and introducing nitrogen. The mixture was melted at 240 °C under nitrogen blanketing and atmospheric pressure and stirred for 20 minutes. The pressure was then reduced to < 1 mbar over 45 minutes, and the mixture was stirred for a further 60 minutes. Phenol was continuously removed during this time. The reaction was then stopped. A light yellow, transparent polymer with a M w of 80,800 g / mol, a glass transition temperature T gof 140 °C and a molar carbonate to urethane ratio of 5:95. 4.7 g of distillate, consisting predominantly of phenol, was obtained (corresponding to 4.1 wt.%, based on the starting materials, product from Example 3 and DPC).

[0205] Example 8: Reaction of Example 4 as UDO component with DPC as carbonyl source in a molar ratio of 1:1.041 (UDO: DPC) in the presence of cat.

[0206] 110.0 g (53.4 mmol, determined from the measured OH number) of the product from Example 4 and 11.9 g (55.6 mmol) of DPC as well as 0.005 g (41 ppm based on the starting materials product from Example 4 and DPC) of catalyst were placed in a flask fitted 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 at 220 °C under a nitrogen blanket and atmospheric pressure and stirred for 20 minutes. The pressure was then reduced to 100 mbar over a period of 10 minutes. The mixture was stirred for 15 minutes at 220 °C, for 15 minutes at 230 °C, and for 10 minutes at 240 °C. Phenol was continuously removed. The pressure was then reduced to < 1 mbar within 35 minutes, and the mixture was stirred for a further 60 minutes. After that, the reaction was stopped. A light yellow, transparent polymer with a M wof 81,200 g / mol, a glass transition temperature T g of 122 °C and a molar carbonate to urethane ratio of 12:88. 9.7 g of distillate, consisting predominantly of phenol, was obtained (corresponding to 8.0 wt.%, based on the starting materials product from Example 4 and DPC).

[0207] Table 2: Comparison of the results of examples 5 to 8.

[0208] * Based on prepolymer and diphenyl carbonate

[0209] **By bending the solidified melt by hand, a first impression was gained. The material is called "ductile" if it did not break during this process. Otherwise, it would be described as "brittle."

[0210] Production of poly(urethane-co-carbonate)s (PUC) - Sequential One-Pot

[0211] Example 9: Reaction of CHDM (according to formula (Ia, 1)) as diol component with H12-MDI (according to formula (Ila, 3)) as diisocyanate building block in a molar ratio of 1.1:1 (diol.diisocyanate) and subsequent reaction with DPC as carhonyl source in a molar ratio of 1.1:1:0.103 (diol.diisocyanate.DPC) with addition of cat.

[0212] 43.0 g (298 mmol) of CHDM was placed in a flask fitted with a Vigreux column, distillation bridge, and dropping funnel. The apparatus was then purged of air and water by alternately evacuating and infusing nitrogen. CHDM was melted at 200 °C under a nitrogen blanket and at atmospheric pressure and stirred for 30 minutes. 71.0 g (271 mmol) of H12-MDI was added via the dropping funnel within a few seconds. The mixture was stirred for 25 minutes at 200 °C, for 25 minutes at 220 °C, for 10 minutes at 230 °C, and for 5 minutes at 240 °C. 5.95 g (28 mmol) of DPC and 0.005 g (42 ppm based on the starting materials CHDM, H12-MDI, and DPC) of catalyst were added in a nitrogen countercurrent. The pressure was then reduced to continuously remove phenol. To do this, the pressure was reduced to < 1 mbar within 60 minutes, and the mixture was condensed for a further 30 minutes. The reaction was then stopped.A light yellow, transparent polymer with an M was obtained. w of 55,600 g / mol, a glass transition temperature T g of 131 °C and a molar carbonate to urethane ratio of 5:95. 4.9 g of distillate, consisting predominantly of phenol, was obtained (corresponding to 3.9 wt.%, based on the starting materials CHDM, H12-MDI, and DPC).

Claims

Patent claims:

1. A process for producing a thermoplastic poly(urethane-co-carbonate), comprising the process steps (i) Reaction of at least one aliphatic diol of formula (Ia) HO — CH2— R 1 - CH2—OH ZT , (la), where each R 1 in formula (Ia) each independently represents an aliphatic group having 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 aliphatic diisocyanate of formula (Ila) where R 2in the formula (Ila) represents a bridging aliphatic structure having 6 to 18 carbon atoms, wherein said bridging structure has at least one cycle and said cycle may optionally contain at least one heteroatom and wherein the bridging structure is attached to the nitrogen atoms shown in structure (Ila) via a secondary or tertiary carbon atom, to a prepolymer and (ii) reacting 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 1.30: 1.0 to 1.01: 1.

0.

2. Process according to claim 1, characterized in that in process step (i) diol of formula (X) and / or diisocyanate of formula (Xi) is also used with HO-R 6 -OH (X), where each R 6 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, when R 6 has at least one cycle, at least one OH group does not belong to a primary alcohol group, OCN-R 7 -NCO (Xi), where each R 7 in the formula (Xi) for - a linear alkylene group with 4 to 12 carbon atoms, - a cycloaliphatic group having 5 to 20, preferably 7 to 18 carbon atoms, but the bonding of the structure R 7 to at least one of the nitrogen atoms shown in structure (Xi) via a primary carbon atom or - an aromatic group with 6 to 18 carbon atoms.

3. Urethanediol prepolymer having a structure of formula (III) where each R 1 in the formula (III) each independently represents an aliphatic group having 4 to 18 carbon atoms, which has at least one cycle and wherein this cycle may optionally contain at least one heteroatom, and wherein the group enclosed by the round brackets -CH2-R'-CH2- also partly independently represents R 6 provided that at least part of the structures is -CH2-R'-CH2-, and R 6 represents an aliphatic alkylene group having 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 6has at least one cycle, is not bound into the chain of the poly(urethane-co-carbonate) via a CH2 group on at least one side, and wherein each R 2 of formula (III) represents a bridging aliphatic structure having 6 to 18 carbon atoms, said bridging structure having at least one cycle and said cycle optionally containing at least one heteroatom and wherein the bridging structure is attached to the nitrogen atoms shown in structure (III) via a secondary or tertiary carbon atom, and wherein the expression R 2 / R 7 means that the group R 2 at least partly also independently of each other for R 7 can be, provided that at least some of the groups R 2 is, and R 7 for - a linear alkylene group with 4 to 12 carbon atoms, - a cycloaliphatic group with 5 to 20 carbon atoms, but the bonding of the structure R 7 to at least one of the nitrogen atoms shown in structure (III) via a primary carbon atom or - an aromatic group with 6 to 18 carbon atoms, where m is the arithmetic mean of the repeating units and is a number > 4.

4. Urethanediol prepolymer according to claim 3, characterized in that the urethanediol prepolymer has an OH number, determined by titration in accordance with DIN EN ISO 4629-2, of 14 to 85 mg KOH / g, where "in accordance" means that pyridine is used instead of the base N-methyl-2-pyrrolidone.

5. Urethanediol prepolymer according to claim 3 or 4, characterized in that the glass transition temperature T g of the urethanediol prepolymer is > 80°C, with the glass transition temperature being determined by means of differential scanning calorimetry.

6. Urethanediol prepolymer according to one of claims 3 to 5, characterized in that the urethanediol prepolymer is prepared according to process step (i) of a process according to one of claims 1 or 2.

7. Urethanediol prepolymer according to one of claims 3 to 6, characterized in that the urethanediol prepolymer has a number-average molecular weight, determined by gel permeation chromatography in tetrahydrofuran with polystyrene as standard, in the range from 1500 to 10,000 g / mol.

8. 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 having 4 to 18 carbon atoms, which has at least one cycle and this cycle may optionally contain at least one heteroatom, and where each R 2of formula (II) each independently represents a bridging aliphatic structure having 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 linked to the nitrogen atoms shown in structure (II) via a secondary or tertiary carbon atom, wherein the wavy lines in formula (I) and (II) each represent the linkage of the structures of formulas (I) and (II) into the chain of the poly(urethane-co-carbonate), and wherein at least some of the structures of formula (I) and (II) are each directly linked to one another to form a urethane group, and at least a further part of the structures (I) is directly linked to one another with at least one further structure of formula (I) to form a carbonate group, characterized in thatthat the thermoplastic poly(urethane-co-carbonate) has > 1 mol-% to < 15 mol-% carbonate groups, based on the sum of the carbonate and urethane groups in the poly(urethane-co-carbonate), wherein the mol-percentages of carbonate and urethane groups are above, 13 C-NMR spectroscopy, and that the thermoplastic poly(urethane-co-carbonate) has a weight average molecular weight of at least 40,000 g / mol.

9. Thermoplastic poly(urethane-co-carbonate) according to claim 8, characterized in that it has no ether groups and / or no ester groups.

10. Thermoplastic poly(urethane-co-carbonate) according to claim 8 or 9, characterized in that the thermoplastic poly(urethane-co-carbonate) has at most 39 mol%, preferably at most 5 mol%, of aromatic groups, this quantity being based on the total amount of aliphatic and aromatic groups.

11. Thermoplastic poly(urethane-co-carbonate) according to any one of claims 8 to 10, comprising the structural formula (IV) where each R 1 has the meanings given for formula (I), where the group -CFF-R'-CFh- enclosed by the round brackets also partly independently of one another represents R 6 provided that at least part of the structures is -CFb-R'-CFb-, and R 6 represents an aliphatic alkylene group having 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 bound into the chain of the poly(urethane-co-carbonate) via a CF group on at least one side, and each R 2 has the meanings given for formula (II), and the expression R 2 / R7 means that the group R 2 at least partly also independently of each other for R 7 can be, provided that at least some of the groups R 2 is, and R 7 for - a linear alkylene group with 4 to 12 carbon atoms, - a cycloaliphatic group with 5 to 20 carbon atoms, but the bonding of the structure R 7 to at least one of the nitrogen atoms shown in structure (IV) via a primary carbon atom or - an aromatic group with 6 to 18 carbon atoms and m is the arithmetic mean of the repeating units and is a number > 4.0 and the wavy lines represent the connection of the structure of formula (IV) into the chain of the poly(urethane-co-carbonate).

12. Thermoplastic poly(urethane-co-carbonate) according to one of claims 8 to 11, characterized in that the thermoplastic poly(urethane-co-carbonate) has a glass transition temperature, determined by means of differential scanning calorimetry, of > 110 °C.

13. Thermoplastic poly(urethane-co-carbonate) according to one of claims 8 to 12, characterized in that the thermoplastic poly(urethane-co-carbonate) has a weight average molecular weight of up to 190,000 g / mol.

13. Thermoplastic poly(urethane-co-carbonate) according to one of claims 8 to 12, characterized in that it is produced by a process according to claim 1 or 2.

14. Process according to claim 1 or 2 or urethanediol prepolymer according to one of claims 3 to 7 or thermoplastic poly(urethane-co-carbonate) according to one of claims 8 to 13, characterized in that R 1in formula (Ia), in formula (I), in formula (III) or in formula (IV) is represented by formula (1) or formula (2), where the positions marked with the stem in formulas (1) and (2) are the positions at which the CIF groups shown in formulas (Ia), (I), (III) and (IV) respectively are located.

15. Process according to claim 1 or 2 or urethanediol prepolymer according to one of claims 3 to 7 or thermoplastic poly(urethane-co-carbonate) according to one of claims 8 to 13, characterized in that the structure R 2 in formula (Ila), (II), (III) or Formula (IV) is represented by one of the formulas (3) to (8), where the positions marked with the star in formulas (3) to (8) are the positions at which the nitrogen atoms shown in formula (IIa), (II), (III) and formula (IV) are located, respectively, and where each R 3in formula (3) independently represents a methyl or ethyl group, p represents 0, 1, or 2 and q represents 0 or 1 and wherein each R 3 in formula (5) independently represents a methyl or ethyl group and p represents 0, 1, or 2.

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