(hetero)cycloaliphatc urethane diol prepolymers

Abstract

The invention relates to an OH-terminated urethane prepolymer with defined build factor, to a process for preparing same and to the use of the prepolymer for polymer preparation.

Description

[0001] (Hetero cycloaliphatic urethanediol prepolymers

[0002] The present invention relates to urethanediol prepolymers, a process for their preparation and the use of the urethanediol prepolymers.

[0003] Aromatic polycarbonates are known for their excellent property profile in terms of mechanical and optical properties, heat resistance, and weathering stability. However, the presence of aromatic groups also imparts certain properties that require improvement, such as transmission, reduced birefringence, and yellowing tendencies. Aliphatic polycarbonates exhibit improved properties in the aforementioned areas that still require improvement, as well as in chemical resistance, but they generally have low glass transition temperatures and an associated lower heat resistance. Therefore, efforts are being made to provide polycarbonates that combine the positive properties of aromatic polycarbonates and aliphatic polycarbonates while, if possible, avoiding the negative properties.

[0004] EP 1 700 877 A1 describes poly(urethane carbonate) polyols obtained using linear aliphatic diols and aliphatic diisocyanates. A molar ratio of diol to diisocyanate of at least 4:1 is always used. The resulting OH-terminated, aliphatic prepolymer is liquid and has a build-up factor m of 1.6. The OH-terminated prepolymer, a polyurethane, is then reacted with diphenyl carbonate together with the unreacted excess diol to obtain the poly(urethane carbonate) polyol with a relatively low molar mass of approximately 1,000 to 2,000 g / mol, as determined from the OH numbers. The resulting poly(urethane carbonate) polyols have glass transition temperatures below 0°C.

[0005] Due to the diverse applications in which polycarbonate can be used, it is clear that it would be of particular interest to be able to use a building block for polycarbonates that opens up a wide range of polycarbonate types and that is ideally easier to handle, transport and / or store than liquids.

[0006] Based on the aforementioned prior art, the object was therefore to provide a polyurethane prepolymer that does not have one or more of the aforementioned disadvantages of liquid (cyclo)aliphatic polyols and / or with which different polymers, in particular polycarbonates or polycarbonate copolymers with different properties, ideally with improved properties compared to pure BPA polycarbonate, can be produced. Surprisingly, it has been found that at least one of these objects is achieved by an OH-terminated urethane prepolymer, i.e., a urethanediol prepolymer with a build-up factor as defined below, having a structure of the formula (I) where each R 1 in the formula (I) each independently represents a group comprising at least one cycle and having 6 to 18 carbon atoms, which is a cycloaliphatic or heterocycloaliphatic group, and wherein each R 2of formula (I) each independently represents a group comprising at least one cycle and having 6 to 18 carbon atoms, which is a cycloaliphatic, aromatic, heterocycloaliphatic or heterocyclic-aromatic group, where m is the arithmetic mean of the repeating units and is a number > 1.7, which is therefore the subject of the present invention.

[0007] The invention also relates to a process for producing a urethanediol prepolymer, preferably a urethane prepolymer, as described above, comprising the process step

[0008] (i) Reaction of one or more diols of formula (II)

[0009] HO - R 1 - OH (II), where R 1in formula (II) represents a group comprising at least one cycle and having 6 to 18 carbon atoms, which is a cycloaliphatic or heterocycloaliphatic group, with one or more diisocyanates of formula (III) where R 2 in formula (III) represents a group comprising at least one cycle with 6 to

[0010] 18 carbon atoms, which is a cycloaliphatic, aromatic, heterocycloaliphatic or heterocyclic-aromatic group, to a urethanediol prepolymer, characterized in that in process step (i) the molar ratio of all diols used to all diisocyanates used is 3.7:1.0 to 1.1:1.0, preferably 3.6:1.0 to 1.1:1.0, likewise preferably 3.5:1.0 to 1.10:1.0, particularly preferably 3.0:1.0 to 1.25:1.0. Such a process, also in the described preferred embodiments and preferences, is preferably used to produce a urethanediol prepolymer, as described above and also below in detail as well as in preferred embodiments. The preferred embodiments and preferences described here and elsewhere for the process or the prepolymer also apply to the prepolymer according to the invention or the process according to the invention.

[0011] It has been shown that these OH-terminated urethane prepolymers, in contrast to the previously known (cyclo)aliphatic polyols, are easier to dose, transport and / or store, since they are not liquids, but usually solids, or at least very highly viscous liquids that can be converted into solids by further processing.

[0012] 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.

[0013] A urethane prepolymer has the urethane group -NH-CO-O-. The buildup factor, designated as "m" in formula (I), indicates how many diisocyanate building blocks the prepolymer is made up of. It is the arithmetic mean of the repeating units found in the square brackets. The buildup factor is upper limited by the fact that it is a "prepolymer", i.e. a reactive building block having terminal OH groups as reactive functionalities. A buildup factor of > 1.7 usually means that the prepolymer is in solid form, which makes it easier to transport, store and meter, for example. With a lower buildup factor, it may still be possible to obtain a useful prepolymer, but it is necessary to remove the excess diol, for example by distillation, if the prepolymer is to be converted into a solid. The buildup factor is preferably > 1.8, more preferably > 1.8.

[0014] The skilled person can determine the arithmetic mean of repeating units m using known methods. In particular, m can be determined by gel permeation chromatography (GPC for short), preferably using the GPC method described below:

[0015] This involves gel permeation chromatography in degassed tetrahydrofuran (THF) as the eluent with a polystyrene 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, which are selected to enable sufficient separation of the molar masses of prepolymers and polymers. Detection is preferably performed via the refractive index (e.g., using an Agilent 1260 Infinity II RID). Calibration is performed using narrowly distributed polystyrene standards (for prepolymers, e.g., ReadyCal Kit Polystyrene low, Part Number: PSS-PSKITR1L, nominal Mp 266-66).000 Da, or for polymers e.g. ReadyCal Kit Polystyrene, Part Number: PSS-PSKITR1, nominal Mp 474-2,520,000 Da). Molar mass averages outside this range are extrapolated. For sample preparation, 20-40 mg of sample are dissolved in 5-10 mL 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 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.

[0016] This results in distinct peaks that can be assigned to corresponding oligomers based on their molecular weight. If the peaks are not clearly separated (especially with longer-chain oligomers), the peaks are preferably subdivided at the nadir between two peaks. If no nadir is measured, the tailing peak is preferably still counted as part of the corresponding repeating unit of the maximum (see also the example section and Figures 2 and 4). The weighted arithmetic mean of the repeating unit m can be calculated from the areas.

[0017] "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 "urethane diol." The skilled person can determine the amount of reactive OH groups using known methods. In particular, the OH groups can be determined by titration as the hydroxyl number (also called OH number) in mg KOH / g. The OH number of the urethane prepolymers is preferably between 10 and 1000 mg KOH / g, more preferably between 20 and 900 mg KOH / g, even more preferably between 30 and 800 mg KOH / g, particularly preferably between 40 and 600 mg KOH / g, and most particularly preferably between 50 and 400 mg KOH / g. The OH number is preferably determined by titration in accordance with DIN EN ISO 4629-2, using pyridine instead of the base N-methyl-2-pyrrolidone. This method is defined by Currenta GmbH & Co. OHG as Method No. 2011-0232602-92D, which can be requested from them.

[0018] R1 includes "cycloaliphatic" and "heterocycloaliphatic" groups having 6 to 18 carbon atoms. "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 ring. The two carbon atoms from which the two hydrogen atoms have been removed can be any, ie, any part of the ring or of the linear alkylene group, if present. Furthermore, the cycloalkylene group according to the present invention can also be bonded to at least one other cycloaliphatic ring via a bridging structure or can be condensed. However, a cycloaliphatic group can also have one or more double bonds.

[0019] 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.

[0020] 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.According to the invention, "aromatic" is preferably understood to mean a group that has at least one cycle of directly bonded carbon atoms with conjugated double bonds. All atoms of the cycle are sp. 2 -hybridized. The electrons are delocalized and obey the Hückel rule.

[0021] A "heterocyclic aromatic group" is preferably understood to mean a group in which, in addition to carbon atoms, at least one heteroatom forms the at least one cycle containing conjugated double bonds. The heteroatom is preferably nitrogen, oxygen, sulfur, or phosphorus.

[0022] It is obvious to the person skilled in the art that, if R 1 in the diol of formula (II) or R 2in the diisocyanate of formula (III) has more than one cycle, one or more carbon atoms of the claimed 6 to 18 carbon atoms can also be part of two or more cycles at the same time.

[0023] The prepolymer according to the invention preferably has a number-average molecular weight M n in the range from 200 to 10,000 g / mol, particularly preferably from 300 to 9,000 g / mol, very particularly preferably from 350 to 8,000 g / mol, extremely preferably from 400 to 7,000 g / mol. This number-average molecular weight M n determined by gel permeation chromatography. The preferred method according to the invention, as explained above, is particularly preferred for this purpose.

[0024] The prepolymer according to the invention preferably has a glass transition temperature T gof > 2°C, particularly preferably > 25°C, most preferably > 30°C, wherein the glass transition temperature is determined by means of dynamic differential calorimetry, preferably in accordance with the standards DIN EN ISO 11357-1:2022-02 and DIN EN ISO 11357-2:2020-08 at a heating rate of 20 K / min. A glass transition temperature > 30°C means that the prepolymer is in solid form at room temperature or the temperatures typically prevailing in the laboratory or production hall and is therefore particularly easy to handle.

[0025] In the process according to the invention, diols are reacted with diisocyanates. This yields a urethane diol prepolymer, which is preferably as described above and below, and more preferably according to the preferred embodiments.

[0026] The diols of formula (II) are preferably those with R 1equal to a cycloaliphatic or heterocycloaliphatic group according to a formula from the following list:

[0027] where the positions marked with an asterisk in formulas (1), (2), (3), (4), (5) and (6) are the positions where the OH groups are located. The diisocyanates of formula (III) are preferably those with R 2 equal to a cycloaliphatic or aromatic group having 6 to 18 carbon atoms according to a formula from the following list: where each R 3 in formula (7) each 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 (9) independently represents a methyl or ethyl group and p represents 0, 1 or 2, where each R 3in formula (14) 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 (15) independently represents a methyl or ethyl group and p represents 0, 1, or 2 and d each independently represents 0 or 1.

[0028] Here, the positions marked with the stem are the positions where the isocyanate groups are located.

[0029] In the process according to the invention, at least one diol of formula (II) and one diisocyanate of formula (III) are used. However, two or more diols of formula (II) and / or two or more diisocyanates of formula (III) can also be used.

[0030] Thus, both for the diols of formula (II) and the diisocyanates of formula (III), it is possible to use not only one compound according to the formulas from the lists described as preferred, but also several compounds according to these lists to prepare a prepolymer according to the invention. It is understood that a preferred diol from the above list can also be used with one or more compounds of formula (II) that are not on the preferred list to prepare the prepolymer, and that a preferred diisocyanate from the list indicated as preferred can also be used with one or more compounds of formula (III) that are not on the preferred list to prepare the prepolymer. However, more preferably, only one preferred diol of formula (II) with R 1 = (1), (2), (3), (4), (5) or (6) and / or a preferred diisocyanate of the formula (III) with R 2 = (7), (8), (9), (10), (11), (12), (13),

[0031] (14) or (15). Particular preference is given to using a preferred diol of the formula (1), (2) or (3) and / or a preferred diisocyanate of the formula (7), (8), (14) or (15). Very particular preference is given to using the diol of the formula (II) used being a diol having a structure according to one of the formulas (1), (2) or (3) and the diisocyanate used being one of the formulas (7), (8), (14) or

[0032] (15), most preferably the diol of formula (II) used is a diol having a structure according to one of the formulas (1) or (2) and the diisocyanate of formula (III) used is one of the formulas (7) or (14). Very particularly preferably R 2 represented by a structure of formula (7), where p = 0 and q = 1.

[0033] Particularly preferably, the structure of formula (7) 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.

[0034] In the structure of formula (14), p is preferably 0 and q is 1, and more preferably, the mixture comprises at least 80 mol% of the structures being 4,4'-diisocyanates. 4,4'-diisocyanate is particularly preferably used as the diisocyanate with structure (14).

[0035] In the structure of formula (15), R 3 preferably methyl, d = 0, p = 1, and more preferably at least 80 mol% is the 2,4-isomer. The 2,4-isomer is particularly preferably used as the diisocyanate with structure (15).

[0036] It is understood that corresponding compounds can exist in the cis, trans, or a mixture of cis and trans forms. For example, the diol of formula (1) is preferably used in the cis form or as a mixture of cis and trans forms.

[0037] To produce a urethanediol prepolymer according to the invention, it is preferable to use no further diol besides the at least one diol of formula (II) and / or no further diisocyanate besides the at least one diisocyanate of formula (III). Particular preference is given to using no further diol besides the one or more diols of formulas (II), (1) to (6), and / or no further diisocyanate besides the one or more diisocyanates of formulas (III), (7) to (15). Very particular preference is given to using only those of formulas (II), (1) to (6) and (III), (7) to (15) as diols and diisocyanates.

[0038] According to these preferences, the urethanediol prepolymer also preferably has only corresponding groups R 1 or R 2 on.

[0039] To produce a urethanediol prepolymer, preferably a prepolymer as defined according to the invention, it is provided according to the invention that at least one corresponding diol of the formula (II) is reacted with at least one corresponding diisocyanate of the formula (III), wherein the molar ratio of all diols used to all diisocyanates used is 3.7:1 to 1.1:1.

[0040] In process step (i), the at least one diol of formula (II) can be initially charged. In this case, the at least one diisocyanate of formula (III) 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 (II) and the at least one diisocyanate (III) 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 80 °C to 250 °C, more preferably from 90 °C to 240 °C, particularly preferably from 100 °C to 230 °C, very particularly preferably from 110 °C to 220 °C. The reaction is exothermic, so that the reaction can preferably also be counter-cooled.If the reaction of process step (i) is already carried out in the presence of at least one further monomer required to produce the target polymer—in the case of poly(urethane-co-carbonate) as the target polymer, in the presence of diaryl carbonate—it is preferable that the temperature is not too high. This allows the reaction of the monomer that reacts with the prepolymer to produce the actual target polymer—i.e., in the case of poly(urethane-co-carbonate) as the target polymer, the reaction of diaryl carbonate—to be minimized. The upper temperature limit in this case is preferably between 90°C and 180°C.

[0041] 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.

[0042] 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.

[0043] As a rule, the viscosity of the mixture increases during process step (i). It is advantageous to carry out thorough mixing in process step (i). In some cases, it may also be advantageous to carry out process step (i) in the presence of a solvent. This is particularly the case when a highly viscous prepolymer is obtained (such as when isosorbide, formula (3), is used as the diol). Aromatic hydrocarbons, particularly preferably chlorobenzene, are preferably used for this purpose. Mixing can also be improved by increasing the temperature. Highly viscous prepolymers are preferably prepared in process step (i) without additional solvent in a heating medium temperature range of 150 °C to 220 °C. It is preferred that no solvent is present in process step (i). This obviates the need for an additional solvent removal step.

[0044] 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. As catalysts, preference can be given to using (A) urea, derivatives of urea and / or (B) the above-mentioned amines and amino ethers, characterized in that the amines and amino ethers contain a functional group which 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 include: (3-dimethylaminopropylamine)urea, 1,1'-((3-.

[0045] (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.

[0046] Particular preference is given to using monobutyltin oxide and / or dibutyltin oxide as catalyst in process step (i). 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.

[0047] In the context of the present invention, ppb and ppm are to be understood as weight-related information unless otherwise stated.

[0048] 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 (II) is generally still present immediately after completion of process step (i), since an excess of diol was used. This diol or these diols, if two or more different diols were used, may still be present during a further process step (ii), which already serves to produce a polymer from the prepolymer. Likewise, the excess diol can also be removed beforehand. Removal of the diol is particularly preferred when the prepolymer is not solid but initially highly viscous. This usually allows the prepolymer to be converted into a solid.

[0049] The urethanediol prepolymer according to the invention is preferably used to produce a polymer. The polymer used for the production of the urethanediol prepolymer, preferably prepared from 1,4-cyclohexanedimethanol (corresponding to formula (1)) and / or tricyclodecanedimethanol (corresponding to formula (2)) as the diol and 1,1'-methylenebis(4-isocyanatocyclohexane) (corresponding to formula (7)) as the sole diisocyanate component or as at least one diisocyanate component used alongside one or more further diisocyanates, is preferably a poly(urethane-co-carbonate), preferably one as described together with its preparation in European Patent Application No. 23217149.6, the content of which is also intended to be the subject of the present application.

[0050] By using, for example, both a (hetero)cycloaliphatic diol and a (hetero)cycloaliphatic diisocyanate, a poly(urethane-co-carbonate) having a high glass transition temperature of at least 90 °C can be obtained from the prepolymer, preferably prepared, for example, from 1,4-cyclohexanedimethanol (corresponding to formula (1)) and / or tricyclodecanedimethanol (corresponding to formula (2)) as the diol and dicyclohexylmethane-4,4'-diisocyanate (corresponding to formula (7)) as the sole diisocyanate component or as at least one diisocyanate component used alongside one or more further diisocyanates, by reaction with, for example, diaryl carbonate. It has also proven particularly advantageous to at least partially remove the (unreacted) aliphatic diol of formula (II) still present after process step (i). This makes it possible to influence the glass transition temperature and increase it further.This allows a targeted adjustment of the glass transition temperature of the target polymer, as described in more detail in European patent application No. 23217149.6.

[0051] The unreacted aliphatic diol of formula (II) 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 (II).

[0052] Preferably, the prepolymer according to the invention obtained from process step (i) is not isolated, but fed directly to its further use. This means that process step (i) is preferably immediately followed by a process step (ii) for converting the prepolymer to the target polymer. This can be achieved, as already described above, for example, by increasing the temperature and applying a vacuum if, for example, in the production of poly(urethane-co-carbonate), the necessary diaryl carbonate and the catalyst are already at least partially present in process step (i). This can also be achieved here by adding the diaryl carbonate and / or the catalyst and increasing the temperature and applying a vacuum.

[0053] Figures:

[0054] Figure 1: GPC spectrum of a prepolymer (Example 5b) based on CHDM and H12-MDI in the used molar ratio of 2:1 (diisocyanate) plotted against the molar mass.

[0055] Figure 2: Illustration of the subdivision of the GPC spectrum of a prepolymer (Example 5b) for determining the arithmetic mean of the repeating unit "m" of the prepolymer and, if applicable, the residual diol content; the designations A to G represent individual peaks that must therefore be considered separately. Figure 3: GPC spectrum of a prepolymer (Example 12) based on TCD-DM and H12-MDI in the molar ratio of 3:1 (diisocyanate) plotted against the molar mass.

[0056] Figure 4: Illustration of the subdivision of the GPC spectrum of a prepolymer (Example 12) for determining the arithmetic mean of the repeating unit "m" of the prepolymer and, if applicable, the residual diol content; the designations A to E represent individual peaks that must therefore be considered separately.

[0057] Figure 5: 13C-NMR spectrum of a poly(urethane-co-carbonate) (Example 35) based on CHDM and H12-MDI in the molar ratio of 2:1 (diisocyanate).

[0058] Examples

[0059] Materials used:

[0060] Diol component (according to formula (II) according to the invention)

[0061] CHDM (1) 1,4-Cyclohexanedimethanol: Mixture of cis-1,4-cyclohexanedimethanol and trancis-1,4-cyclohexanedimethanol, CAS: 105-08-8, 99%, Sigma Aldrich, Germany, was used without further purification

[0062] Zrans-CHDM (1) trans-} ,4-Cyclohexanedimethanol, CAS: 3236-48-4, 97.77%, BLDpharm, China, was used without further purification

[0063] TCD-DM (2) Tricyclodecanedimethanol: mixture of isomers, CAS: 26896-48-0, 96%, Sigma-Aldrich, Germany, was used without further purification

[0064] ISB (3) Polysorb PS A: Isosorbide, CAS: 652-67-5, 99.8%, Roquette Freres, France, was used without further purification

[0065] TMCBD (4) 2,2,4,4-Tetramethylcyclobutane-l,3-diol: mixture of isomers, CAS: 3010-96-6,

[0066] 99%, BASF SE, Germany, was used without further purification

[0067] H12-BPA (5) Hydrogenated Bisphenol A: 4,4'-Isopropylidenedicyclohexanol, mixture of isomers, CAS: 80-04-6, 90%, Sigma-Aldrich, Germany, was used without further purification

[0068] THF-DM (6) 2, 5 -tetrahydrofuranimethanol, isomer mixture, CAS: 104-80-3, 99%,

[0069] Sugar Energy, China, was used without further purification Diol component (comparison)

[0070] HD 1,6-Hexanediol, CAS: 629-11-8, 97%, Sigma Aldrich, Germany, was used without further purification

[0071] Diisocyanate component (according to formula (III) according to the invention)

[0072] H12-MDI (7) Dicyclohexylmethane-4,4'-diisocyanate (Dicyclohexylmethane-2,4'-diisocyanate (<

[0073] 10 wt.%) and dicyclohexylmethane-2,2'-diisocyanate (< 2 wt.%): mixture of cis- and trans-isomers), CAS: 5124-30-1 (based on 4,4'-isomer), Covestro AG, Germany, was used without further purification

[0074] IPDI (8) Isophorone diisocyanate: Mixture of czs-isophorone diisocyanate and trans-isophorone diisocyanate, CAS: 4098-71-9, Covestro AG, Germany, was used without further purification

[0075] H6-mXDI (13) 1,3-bis(isocyanatomethyl)cyclohexane, mixture of isomers, CAS: 38661-72-2, 99%, Sigma-Aldrich, Germany, was used without further purification

[0076] MDI (14) Diphenylmethane-4,4'-diisocyanate, CAS: 101-68-8, Covestro AG, Germany, was stored at 45°C and used without further purification

[0077] TDI (15) Toluene-2,4-diisocyanate, CAS: 584-84-9, Covestro AG, Germany, was used without further purification

[0078] Diisocyanate component (comparison)

[0079] HDI hexamethylene diisocyanate, CAS: 822-06-0, Covestro AG, Germany, was used without further purification

[0080] Carbonyl source (for use of the urethanediol prepolymer for PUC production)

[0081] DPC Diphenyl Carbonate, CAS: 102-09-0, Covestro AG, Germany, was

[0082] Use freshly distilled

[0083] Catalyst (for use of the urethanediol prepolymer for PUC production)

[0084] Cat Monobutyltin oxide, CAS: 2273-43-0, TIB Chemicals AG, Germany, was used without further purification. Analytical methods:

[0085] GPC:

[0086] 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.

[0087] Determination of the arithmetic mean of the repeating unit m in prepolymers using examples 5b and 12

[0088] 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 m (see, for example, also formula (I)), 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 5b in Figure 1). The determination of this arithmetic mean of the repeating unit m and the residual diol amount is explained below using Example 5b.

[0089] Both the m of the prepolymers and the remaining unreacted diol in wt. % were determined from the GPC spectra plotted against the elution volume (Figures 1 and 3). 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 peaks were subdivided at the nadir between two peaks until no more nadir was measured (as seen in the GPC spectra of Examples 5b and 12 in Figures 2 and 4, respectively).

[0090] The GPC spectrum in Figure 2 for Example 5b yielded the following areas F (in %): A: Prepolymer with repeating unit m = 5 (F = 12.4%) (here it is evident that oligomers with a higher repeating unit are also included, the value is nevertheless artificially designated as “5”)

[0091] B: Prepolymer with repeating unit m = 4 (F = 9.9%)

[0092] C: Prepolymer with repeating unit m = 3 (F = 15.3%)

[0093] D: Prepolymer with repeating unit m = 2 (F = 22.4%)

[0094] E: Prepolymer with repeating unit m = 1 (F = 27.7%)

[0095] F: unknown (F = 0.3%)

[0096] G: Residual diol CHDM (F = 12.0%)

[0097] According to the weighted arithmetic mean, m was determined.

[0098] 1 x F(m = 1) + 2 x F(m = 2) + + nx (F(m = ri) m = -

[0099] F (prepolymer)

[0100] With F(prepolymer) = 87.7%

[0101] 1 x 27.7 + 2 x 22.4 + 3 x 15.3 + 4 x 9.9 + 5 x 12.4 m = - — — - = 2.5

[0102] 87.7

[0103] The arithmetic mean of the repetition unit “m” for example 5b is 2.5.

[0104] 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 each other in the GPC spectrum due to the low resolution.

[0105] It is also clear to the person skilled in the art that with a higher excess of diol component, m becomes smaller and the proportion of unreacted monomer diol becomes larger, as shown below in Example 12 (see Figure 3).

[0106] The GPC spectrum in Figure 4 for Example 12 yielded the following areas F (in %):

[0107] A: Prepolymer with repeating unit m = 4 (F = 6.3%) (here it is evident that oligomers with a higher repeating unit are also included, the value is nevertheless artificially designated as “4”, see above)

[0108] B: Prepolymer with repeating unit m = 3 (F = 9.7%)

[0109] C: Prepolymer with repeating unit m = 2 (F = 20.1%)

[0110] D: Prepolymer with repeating unit m = 1 (F = 35.5%)

[0111] E: residual diol TCD-DM (F = 28.4%)

[0112] According to the weighted arithmetic mean, m was determined. With F(prepolymer) = 71.6%

[0113] 1 x 24.8 + 2 x 4.9 + 3 x 0.7 m = - 7771.76 - = l' 8

[0114] The arithmetic mean of the repeating unit “m” for example 12 is 1.8.

[0115] It is also clear to the person skilled in the art that the use of two or more different diisocyanates makes the calculation of the arithmetic mean of the repeating unit m more difficult due to the overlap of peaks of different oligomer structures, in particular due to the use of diisocyanates with very different molecular weights (e.g. H12-MDI and TDI). In these cases, a clear assignment of the oligomers by GPC is not possible, so that the arithmetic mean of the repeating unit m can only be determined approximately (represented by a However, if diisocyanates of similar molecular weight are used (e.g. H12-MDI and MDI), the evaluation of the arithmetic mean of the repeating unit m can be carried out as described above, since the resolution of the GPC spectrum is not sufficient to separate the different oligomers.

[0116] DSC:

[0117] The glass transition temperature (T g ) was determined as the inflection point in the second heating process by means of 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.

[0118] 13 C NMR spectroscopy:

[0119] The ratio of urethane to carbonate groups in the poly(urethane-co-carbonate)s was determined by ,3 C 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.

[0120] Measurement parameters:

[0121] Pulse program pulprog zgig30

[0122] Scan per increment NS: 512

[0123] Relaxation time between two scans Dl: 4 see

[0124] The following illustrates the evaluation of the urethane to carbonate group ratio using example 35 of a poly(urethane-co-carbonate) made from 1,4-cyclohexanedimethanol (CHDM) and H12-MDI in a molar ratio of 2:1 (diisocyanate). Reference is made to Figure 5.

[0125] Assignment for the determination of urethane to carbonate from the 13 C NMR spectrum

[0126] Urethane signal at 156 ppm Carbonate signal at 155.5 ppm

[0127] The molar ratio results directly from the areas of the respective signals normalized to 100.

[0128] From the 13 C-NMR spectrum in Figure 5 gives the following estimated molar ratio: Urethane = 65

[0129] Carbonate = 35

[0130] Hydroxyl number:

[0131] The hydroxyl number (also called OH number) was determined titrimetrically by Currenta GmbH & Co. OHG in accordance with DIN EN ISO 4629-2. However, pyridine was used instead of the base specified 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.

[0132] NCO value:

[0133] The NCO content was determined titrimetrically according to DIN EN ISO 11909:2007-05.

[0134] Production of urethane diol prepolymers (UDO)

[0135] Example 1: Reaction of CHDM (according to formula (II), (1)) as diol component with H12-MDI (according to formula (III), (7)) as diisocyanate building block in a molar ratio of 1.1:1 (diol:diisocyanate).

[0136] 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 a nitrogen blanket 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 n of 5780 g / mol.

[0137] Example 2: Reaction of CHDM (according to formula (II), (1)) as the diol component with H12-MDI (according to formula (III), (7)) as the diisocyanate building block in a molar ratio of 1.25:1 (diol:diisocyanate). 103.0 g (714 mmol) of CHDM were placed in a flask equipped with a reflux condenser and a dropping funnel. The apparatus was then freed of traces 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 at 180 °C for 30 minutes. After 30 minutes, a sample was taken for NCO measurement in a nitrogen counterflow. The NCO value was 0%, and the batch was stopped.A colorless, transparent prepolymer with an OH number of 62.8 mg KOH / g and a glass transition temperature T was obtained. g of 97 °C and a molecular weight M n of 2790 g / mol.

[0138] Example 3: Reaction of CHDM (according to formula (1)) as diol component with H12-MDI (according to formula (7)) as diisocyanate building block in a molar ratio of 3:2 (diol:diisocyanate) in the presence of cat.

[0139] 123.75 g (858 mmol) of CHDM and 0.015 g (100 ppm based on H12-MDI) of catalyst were placed in a flask fitted with a reflux condenser and a dropping funnel. The mixture was melted under a nitrogen blanket and heated to 100 °C at atmospheric pressure with stirring. 150 g (572 mmol) of H12-MDI were added dropwise via the dropping funnel over a period of 2 h at 100 °C. The temperature was then raised to 130 °C, and the mixture was stirred for 60 minutes at 130 °C. After 60 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 118.3 mg KOH / g and a glass transition temperature of T was obtained. g of 62 °C and a molecular weight M n of 1630 g / mol.

[0140] Example 4: Reaction of CHDM (according to formula (II), (1)) as diol component with H12-MDI (according to formula (III), (7)) as diisocyanate building block in a molar ratio of 1.75:1 (diol:diisocyanate).

[0141] 96.25 g (667 mmol) of CHDM and 100.0 g (381 mmol) of H12-MDI were placed in a flask fitted with a reflux condenser. The mixture was melted under a nitrogen blanket and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred for 2 h at 130 °C. After 2 h, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A colorless, transparent prepolymer with an OH number of 154.7 mg KOH / g and a glass transition temperature of T was obtained. g of 55 °C and a molecular weight M n of 1070 g / mol.

[0142] Example 5a: Reaction of CHDM (according to formula (II), (1)) as the diol component with H12-MDI (according to formula (III), (7)) as the diisocyanate building block in a molar ratio of 2:1 (diol:diisocyanate). 660 g (4.58 mol) of CHDM and 600 g (2.29 mol) of H12-MDI were placed in a flask fitted with a reflux condenser. The mixture was melted under a nitrogen blanket and heated to 130 °C at atmospheric pressure with stirring. The mixture was stirred for 2 h at 130 °C. After 2 h, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A colorless, transparent prepolymer with an OH number of 207.7 mg KOH / g and a glass transition temperature T g of 36 °C and a molecular weight M n of 830 g / mol.

[0143] Example 5b: Reaction of CHDM (according to formula (II), (1)) as diol component with H12-MDI (according to formula (III), (7)) as diisocyanate building block in a molar ratio of 2:1 (diol:diisocyanate) in the presence of cat.

[0144] 440 g (3.05 mol) of CHDM and 0.04 g (100 ppm based on H12-MDI) of catalyst were placed in a flask fitted with a reflux condenser and a dropping funnel. The mixture was melted under a nitrogen blanket and heated to 130 °C at atmospheric pressure with stirring. 400 g (1.525 mol) of H12-MDI were added dropwise via the dropping funnel over a period of 3 h at 130 °C. The mixture was then stirred for 4 h at 130 °C. After 4 h, 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 204.7 mg KOH / g and a glass transition temperature T g of 35 °C and a molecular weight M n of 780 g / mol.

[0145] Example 6: Reaction of CHDM (according to formula (II), (1)) as diol component with H12-MDI (according to formula (III), (7)) as diisocyanate building block in a molar ratio of 3:1 (diol. diisocyanate).

[0146] 330 g (2.29 mol) of CHDM and 200 g (0.762 mol) of H12-MDI were placed in a flask fitted with a reflux condenser. The mixture was melted under a nitrogen blanket and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 2 h. After 2 h, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A colorless, transparent prepolymer was obtained with an OH number of 314.5 mg KOH / g and a glass transition temperature T g of 4 °C and a molecular weight M n of 550 g / mol.

[0147] Example 7: Reaction of trans-CHDM (according to formula (II), (1)) as diol component with H12-MDI (according to formula (III), (7)) as diisocyanate building block in a molar ratio of 2:1 (diol:diisocyanate).

[0148] 50.0 g (0.35 mol) of trans-CHDM and 45.45 g (0.17 mol) of H12-MDI were placed in a flask fitted with a reflux condenser. The mixture was melted under a nitrogen blanket and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 2 h. After 2 h, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A colorless, transparent prepolymer with an OH number of 189.5 mg KOH / g and a glass transition temperature of T was obtained. g of 53 °C and a molecular weight M n of 930 g / mol.

[0149] Example 8: Reaction of TCD-DM (according to formula (II), (2)) as diol component with H12-MDI (according to formula (III), (7)) as diisocyanate building block in a molar ratio of 1.1:1 (DioLDiisocyanate).

[0150] 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.

[0151] Example 9: Reaction of TCD-DM (according to formula (II), (2)) as diol component with H12-MDI (according to formula (III), (7)) as diisocyanate building block in a molar ratio of 1.25:1 (diol:diisocyanate).

[0152] 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 infusing nitrogen. The mixture was melted at 200 °C under a nitrogen blanket and at 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 was obtained with an OH number of 54.5 mg KOH / g and a glass transition temperature of T gof 104 °C and a molecular weight M n of 2300 g / mol.

[0153] Example 10: Reaction of TCD-DM (according to formula (II), (2)) as diol component with H12-MDI (according to formula (III), (7)) as diisocyanate building block in a molar ratio of 3:2 (DiokDiisocyanat).

[0154] 112 g (0.57 mol) of TCD-DM and 100 g (2.29 mol) of H12-MDI were placed in a flask fitted with a reflux condenser. The mixture was melted under a nitrogen blanket and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 170 °C for 2 h. After 2 h, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A colorless, transparent prepolymer was obtained with an OH number of 104.4 mg KOH / g and a glass transition temperature of T g of 91 °C and a molecular weight M n of 1200 g / mol.

[0155] Example 11: Reaction of TCD-DM (according to formula (II), (2)) as diol component with H12-MDI (according to formula (III), (7)) as diisocyanate building block in a molar ratio of 2:1 (diol:diisocyanate).

[0156] 300 g (1.53 mol) of TCD-DM and 200 g (0.76 mol) of H12-MDI were placed in a flask fitted with a reflux condenser. The mixture was melted under a nitrogen blanket and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 2 h. After 2 h, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A colorless, transparent prepolymer with an OH number of 170.9 mg KOH / g and a glass transition temperature of T g of 53 °C and molecular weight M n of 750 g / mol.

[0157] Example 12: Reaction of TCD-DM (according to formula (II), (2)) as diol component with H12-MDI (according to formula (III), (7)) as diisocyanate building block in a molar ratio of 3:1 (DioLDiisocyanate).

[0158] 157 g (0.80 mol) of TCD-DM and 70 g (0.27 mol) of H12-MDI were placed in a flask fitted with a reflux condenser. The mixture was melted under a nitrogen blanket and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 2 h. After 2 h, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A colorless, transparent prepolymer was obtained with an OH number of 263.0 mg KOH / g and a glass transition temperature T g of 37 °C and a molecular weight M n of 420 g / mol.

[0159] Example 13: Reaction of ISB (according to formula (II), (3)) as diol component with H12-MDI (according to formula (III), (7)) as diisocyanate building block in a molar ratio of 2:1 (diol:diisocyanate).

[0160] 59 g (404 mmol) of ISB and 53 g (202 mmol) of H12-MDI were placed in a flask fitted with a reflux condenser. The apparatus was then freed of traces of air and water by alternately evacuating and introducing nitrogen. The mixture was then melted under a nitrogen blanket and heated to 180 °C at atmospheric pressure with stirring. After stirring for 3.5 h at 180 °C under a nitrogen blanket, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 194.9 mg KOH / g and a glass transition temperature T g of 73 °C and a molecular weight M n of 660 g / mol.

[0161] Example 14: Reaction of TMCBD (according to formula (II), (4)) as the diol component with H12-MDI (according to formula (III), (7)) as the diisocyanate building block in a molar ratio of 2:1 (diol:diisocyanate). 66 g (458 mmol) of TMCBD and 60 g (229 mmol) of H12-MDI were placed in a flask equipped with a reflux condenser. The apparatus was then freed of traces of air and water by alternately evacuating and introducing nitrogen. The mixture was then melted under a nitrogen blanket and heated to 180 °C at atmospheric pressure with stirring. After 1.5 h of stirring at 180 °C under a nitrogen blanket, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A yellowish, transparent prepolymer with an OH number of 190.0 mg KOH / g and a glass transition temperature T g of 77 °C and a molecular weight M n of 1060 g / moL

[0162] Example 15: Reaction of H12-BPA (according to formula (II), (5)) as diol component with H12-MDI (according to formula (III), (7)) as diisocyanate building block in a molar ratio of 2:1 (diol. diisocyanate).

[0163] 82.5 g (343 mmol) of H12-BPA and 45.0 g (172 mmol) of H12-MDI were placed in a flask fitted with a reflux condenser. The mixture was melted under a nitrogen blanket and heated to 160 °C at atmospheric pressure with stirring. After stirring for 2 h at 160 °C under a nitrogen blanket, the reaction was stopped. A yellowish, transparent prepolymer with an OH number of 74.0 mg KOH / g and a glass transition temperature of T g of 96 °C and a molecular weight M n of 930 g / mol.

[0164] Example 16: Reaction of THF-DM (according to formula (II), (6)) as diol component with H12-MDI (according to formula (III), (7)) as diisocyanate building block in a molar ratio of 2:1 (diol:diisocyanate).

[0165] 67 g (507 mmol) of THF-DM was placed in a flask fitted with a reflux condenser and a dropping funnel. The apparatus was then freed of traces of air and water by alternately evacuating and introducing nitrogen. The mixture was melted at 150 °C under nitrogen blanketing and atmospheric pressure and stirred for 30 minutes. 66.5 g (253 mmol) of H12-MDI was added via the dropping funnel within a few seconds. After stirring for 1 h at 150 °C under nitrogen blanketing, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 202.1 mg KOH / g and a glass transition temperature T g of 27 °C and a molecular weight M n of 680 g / mol.

[0166] Example 17: Reaction of CHDM (according to formula (II), (1)) as diol component with IPDI (according to formula (III), (8)) as diisocyanate building block in a molar ratio of 2:1 (diol:diisocyanate).

[0167] 74 g (513 mmol) of CHDM and 57 g (256 mmol) of IPDI were placed in a flask fitted with a transition piece and hose connection to create a vacuum. The apparatus was then purged of any traces of air and water by alternately evacuating and introducing nitrogen. The mixture was then melted under a nitrogen blanket and heated to 150 °C at atmospheric pressure with stirring. The mixture was stirred for 1 h at 150 °C. After 2 h, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A yellowish, transparent prepolymer with an OH number of

[0168] 219.6 mg KOH / g, a glass transition temperature T g of 43 °C and a molecular weight M nof 700 g / mol.

[0169] Example 18: Reaction of CHDM (according to formula (II), (1)) as diol component with H6-mXDI (according to formula (III), (13)) as diisocyanate building block in a molar ratio of 2:1 (Dio diisocyanate).

[0170] 150 g (1.04 mol) of CHDM and 101 g (0.52 mol) of H6-mXDI were placed in a flask fitted with a reflux condenser. The mixture was melted under a nitrogen blanket and heated to 130 °C at atmospheric pressure with stirring. After 2 h of stirring at 130 °C under a nitrogen blanket, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 233.2 mg KOH / g and a glass transition temperature of T g of 32 °C and a molecular weight M n of 700 g / mol.

[0171] Example 19: Reaction of HD (comparison) as diol component with H12-MDI (according to formula (III), (7)) as diisocyanate building block in a molar ratio of 2:1 (DioLDiisocyanate).

[0172] 55 g (465 mmol) of HD and 61 g (233 mmol) of H12-MDI were placed in a flask fitted with a reflux condenser. The apparatus was then purged of air and water by alternately evacuating and introducing nitrogen. The mixture was then melted under a nitrogen blanket and heated to 130 °C at atmospheric pressure with stirring. After 1 h of stirring at 130 °C under a nitrogen blanket, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A colorless, transparent prepolymer with an OH number of

[0173] 235.6 mg KOH / g, a glass transition temperature T g of -2 °C and a molecular weight M„ of 960 g / mol.

[0174] Example 20: Reaction of CHDM (according to formula (II), (1)) as diol component with HDI (comparison) as diisocyanate building block in a molar ratio of 2:1 (diol:diisocyanate).

[0175] 84 g (582 mmol) of CHDM and 49 g (291 mmol) of HDI were placed in a flask fitted with a reflux condenser. The apparatus was then purged of any traces of air and water by alternately evacuating and introducing nitrogen. The mixture was then melted under a nitrogen blanket and heated to 130 °C at atmospheric pressure with stirring. After stirring for 1 h at 130 °C under a nitrogen blanket, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A colorless, cloudy prepolymer was obtained with an OH number of 244.4 mg KOH / g and a glass transition temperature of T g of -2 °C and a molecular weight M n of 430 g / mol.

[0176] Table 1: Comparison of the results of examples 1 to 20. of urethanediol under aromatic iExample 21: Reaction of CHDM (according to formula (II), (1)) as diol component with H12-MDI

[0177] (according to formula (III), (7), A) and MDI (according to formula (III), (14), B) in a weight ratio of 9:1 as diisocyanate building blocks in a molar ratio of 2:1 (diol:diisocyanates A+B).

[0178] 110.5 g (0.77 mol) of CHDM, 90 g (0.34 mol) of H12-MDI, and 10 g (0.04 mol) of MDI were placed in a flask fitted with a reflux condenser. The mixture was melted under a nitrogen blanket and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred for 1 h at 130 °C. After 1 h, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 192.3 mg KOH / g and a glass transition temperature of T gof 49 °C and a molecular weight M n of 820 g / mol.

[0179] 22: Reaction of CHDM (according to formula (II), (1)) as diol component with H12-MDI

[0180] (according to formula (III), (7), A) and MDI (according to formula (III), (13), B) in a weight ratio of 1:1 as diisocyanate building blocks in a molar ratio of 2:1 (DiokDiisocyanate A+B).

[0181] 59.85 g (0.41 mol) of CHDM, 25 g (0.10 mol) of H12-MDI, and 25 g (0.11 mol) of MDI were placed in a flask fitted with a reflux condenser. The mixture was melted under a nitrogen blanket and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 1 h. After 1 h, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 210.9 mg KOH / g and a glass transition temperature T g of 44 °C and a molecular weight and Mn of 790 g / mol.

[0182] 23: Reaction of CHDM (according to formula (II), (1)) as diol component with H12-MDI

[0183] (according to formula (III), (7), A) and MDI (according to formula (III), (14), B) in a weight ratio of 1:9 as diisocyanate building blocks in a molar ratio of 2:1 (DiokDiisocyanate A+B).

[0184] 57.4 g (398 mmol) of CHDM, 5 g (19 mmol) of H12-MDI, and 45 g (180 mmol) of MDI were placed in a flask fitted with a reflux condenser. The mixture was melted under a nitrogen blanket and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred for 1 h at 130 °C. After 1 h, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 129.9 mg KOH / g and a glass transition temperature of T g of 49 °C and a molecular weight M nof 960 g / mol. Example 24: Reaction of CHDM (according to formula (II), (1)) as the diol component with H12-MDI (according to formula (III), (7), A) and TDI (according to formula (III), (15), B) in a weight ratio of 9:1 as diisocyanate building blocks in a molar ratio of 2:1 (diol:diisocyanate A+B).

[0185] 115.5 g (0.80 mol) of CHDM, 90 g (0.34 mol) of H12-MDI, and 10 g (0.06 mol) of TDI were placed in a flask fitted with a reflux condenser. The mixture was melted under a nitrogen blanket and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred for 1 h at 130 °C. After 1 h, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 198.8 mg KOH / g and a glass transition temperature of T g of 43 °C and a molecular weight M n of 750 g / mol.

[0186] Example 25: Reaction of CHDM (according to formula (II), (1)) as diol component with H12-MDI (according to formula (III), (7), A) and TDI (according to formula (III), (15), B) in a weight ratio of 1:1 as diisocyanate building blocks in a molar ratio of 2:1 (diol:diisocyanate A+B).

[0187] 137.8 g (0.96 mol) of CHDM, 50 g (0.19 mol) of H12-MDI, and 50 g (0.29 mol) of TDI were placed in a flask fitted with a reflux condenser. The mixture was melted under a nitrogen blanket and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 1 h. After 1 h, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 206.8 mg KOH / g and a glass transition temperature of T g of 46 °C and a molecular weight M n of 740 g / mol.

[0188] Example 26: Reaction of CHDM (according to formula (II), (1)) as diol component with H12-MDI (according to formula (III), (7), A) and TDI (according to formula (III), (15), B) in a weight ratio of 1:9 as diisocyanate building blocks in a molar ratio of 2:1 (diol:diisocyanate A+B).

[0189] 160 g (1.1 mol) of CHDM, 10 g (38 mmol) of H12-MDI, and 90 g (517 mmol) of TDI were placed in a flask fitted with a reflux condenser. The mixture was melted under a nitrogen blanket and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred for 1 h at 130 °C. After 1 h, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 205.6 mg KOH / g and a glass transition temperature T g of 45 °C and M n of 740 g / mol.

[0190] Example 27: Reaction of CHDM (according to formula (II), (1)) as the diol component with MDI (according to formula (III), (14)) as the diisocyanate building block in a molar ratio of 1.1:1 (diol:diisocyanate). 103 g (714 mmol) of CHDM was placed in a flask equipped with a reflux condenser and a dropping funnel. The apparatus was then freed of traces of air and water by alternately evacuating and introducing nitrogen. CHDM was melted at 200 °C under a nitrogen blanket and at atmospheric pressure and stirred for 30 minutes. 143 g (571 mmol) of MDI was added via the dropping funnel within a few seconds. After 10 minutes of stirring at 200 °C under a nitrogen blanket, followed by a ten-minute hold phase at 220 °C and a ten-minute hold phase at 240 °C, the reaction mixture was stopped. A yellowish, transparent prepolymer with an OH number of 29.2 mg KOH / g and a glass transition temperature T g of 123 °C and a molecular weight M nof 6830 g / mol.

[0191] Example 28: Reaction of CHDM (according to formula (II), (1)) as diol component with MDI (according to formula (III), (14)) as diisocyanate building block in a molar ratio of 1.25:1 (diol:diisocyanate).

[0192] 103 g (714 mmol) of CHDM was 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. 143 g (571 mmol) of MDI was added via the dropping funnel within a few seconds. After stirring for 10 minutes at 200 °C under a nitrogen blanket, followed by a five-minute holding phase at 220 °C, the reaction was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 65.0 mg KOH / g and a glass transition temperature T gof 105 °C and a molecular weight M n of 2940 g / mol.

[0193] Example 29: Reaction of CHDM (according to formula (II), (1)) as diol component with MDI (according to formula (III), (14)) as diisocyanate building block in a molar ratio of 3:2 (DioLDiisocyanate).

[0194] 115 g (797 mmol) of CHDM was 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. 133 g (531 mmol) of MDI was added via the dropping funnel within a few seconds. After stirring for 10 minutes at 200 °C under nitrogen blanketing, the reaction mixture was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 114.2 mg KOH / g and a glass transition temperature of T gof 80 °C and a molecular weight M n of 1650 g / mol.

[0195] Example 30: Reaction of CHDM (according to formula (II), (1)) as diol component with MDI (according to formula (III), (14)) as diisocyanate building block in a molar ratio of 2:1 (DioLDiisocyanate).

[0196] 264 g (1831 mmol) of CHDM was placed in a flask fitted with a reflux condenser and a dropping funnel. The apparatus was then freed of air and water traces by alternately evacuating and introducing nitrogen. The mixture was melted at 200 °C under nitrogen blanketing and atmospheric pressure and stirred for 30 minutes. 229 g (915 mmol) of MDI was added via the dropping funnel within a few seconds. After stirring for 10 minutes at 200 °C under nitrogen blanketing, the reaction was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 203.5 mg KOH / g and a glass transition temperature of T gof 44 °C and a molecular weight M n of 940 g / mol.

[0197] Example 31: Reaction of CHDM (according to formula (II), (1)) as diol component with TDI (according to formula (III), (15)) as diisocyanate building block in a molar ratio of 2:1 (diol:diisocyanate).

[0198] 82.8 g (574 mmol) of CHDM and 50 g (287 mmol) of TDI were placed in a flask fitted with a reflux condenser. The apparatus was then freed of traces of air and water by alternately evacuating and introducing nitrogen. The mixture was melted at 80 °C under a nitrogen blanket and at atmospheric pressure. The mixture was heated to 130 °C over a period of 40 minutes. After 60 minutes at 130 °C, a sample was taken for NCO measurement in a nitrogen countercurrent. The NCO value was 0%, and the reaction was stopped. A yellowish, transparent prepolymer was obtained with an OH number of 245.5 mg KOH / g and a glass transition temperature of T gof 39 °C and a molecular weight Mn of 710 g / mol.

[0199] Table 2: Comparison of the results of examples 21 to 31. Production of urethanediol prepolymers (UDO) with subsequent distillation of the unreacted

[0200] Monomer-diols

[0201] Example 32: Reaction of CHDM (according to formula (II), (1)) as diol component with H12-MDI (according to formula (III), (7)) as diisocyanate building block in a molar ratio of 2:1 (diol.diisocyanate) in the presence of catalyst with subsequent distillation of the excess CHDM.

[0202] 440 g (3.05 mol) of CHDM and 0.040 g (100 ppm based on H12-MDI) of catalyst were placed in a flask equipped with a reflux condenser and a dropping funnel. The mixture was melted under a nitrogen blanket and heated to 100 °C at atmospheric pressure with stirring. 400 g (1.52 mmol) of H12-MDI were added dropwise via the dropping funnel over a period of 3 h at 130 °C. The temperature was then increased to 130 °C, and the mixture was stirred for 4 h at 130 °C. The reaction was stopped, and the mixture remained in the flask overnight. Distillation was carried out the next day. For this purpose, the dropping funnel and reflux condenser were removed, and a Vigreux column with a connected distillation bridge was installed. The distillation of the unreacted monomer-diol CHDM was carried out under reduced pressure (< 1 mbar) at a bath temperature of 180 °C. After completion of the distillation, a yellowish, transparent prepolymer was obtained with an OH number of 137.7 mg KOH / g and a glass transition temperature Tg of 34 °C and a molecular weight M n of 1130 g / mol.

[0203] Example 33: Reaction of CHDM (according to formula (II), (1)) as diol component with H12-MDI (according to formula (III), (7)) as diisocyanate building block in a molar ratio of 3:1 (DiokDiisocyanat) in the presence of Kat with subsequent distillation of the excess CHDM.

[0204] 330 g (2.29 mol) of CHDM and 0.020 g (100 ppm based on H12-MDI) of catalyst were placed in a flask fitted with a reflux condenser and a dropping funnel. The mixture was melted under a nitrogen blanket and heated to 100 °C with stirring at atmospheric pressure. 200 g (0.76 mmol) of H12-MDI were added dropwise via the dropping funnel over a period of 2 h at 100 °C. The temperature was then increased to 130 °C, and the mixture was stirred for 2 h at 130 °C. After 2 h, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%. The reaction was stopped, and the mixture remained in the flask overnight. Distillation was carried out the next day. For this purpose, the dropping funnel and reflux condenser were removed, and a Vigreux column with a connected distillation bridge was installed. The distillation of the unreacted monomer-diol CHDM was carried out under reduced pressure (< 1 mbar) at a bath temperature of 175 °C.After completion of the distillation, a yellowish, transparent prepolymer with an OH number of 118.3 mg KOH / g and a glass transition temperature T was obtained. g of 63 °C and a molecular weight M n of 1660 g / mol. Table 3: Comparison of the results of Examples 32 and 33.

[0205] Production of poly(urethane-co-carbonaf)ene (PUC) by polycondensation of previously prepared urethanediol prepolymers (UDO) with diphenyl carbonate (PPC)

[0206] Example 34: Reaction of Example 3 as UDO component with DPC as carbonyl source in a molar ratio of 1:1 (UDO: DPC) in the presence of cat.

[0207] 75.0 g (79.1 mmol, amount of substance calculated from the OH number) of Example 3 (OH number: 118.3 mg KOH / g) and 16.94 g (79.1 mmol) of DPC as well as 0.002 g (22 ppm based on the starting materials Example 3 and DPC) of catalyst were placed in a flask fitted with a Vigreux column and distillation bridge. The mixture was melted under a nitrogen blanket and heated to 150 °C at atmospheric pressure with stirring. The mixture was stirred for 30 minutes at 150 °C and for 20 minutes at 190 °C. A vacuum was then applied. The pressure was reduced to 100 mbar over 10 minutes, with phenol continuously removed. Stirring was continued at 100 mbar for approximately 60 minutes. The bath temperature was then heated to 220 °C in 10 °C increments, each with a ten-minute holding phase. The pressure was then reduced to < 1 mbar and condensation continued for another 60 minutes. After that, the reaction was stopped. A light yellow, transparent polymer with a M w of 72,600 g / mol.

[0208] Example 35: Reaction of Example 5a as UDO component with DPC as carbonyl source in a molar ratio of 1:1.03 (UDO: DPC) in the presence of cat.

[0209] 150.0 g (277.6 mmol, amount calculated from the OH number) of Example 5a (OH number: 207.7 mg KOH / g) and 61.34 g (286.3 mmol) of DPC, as well as 0.008 g (38 ppm based on the starting materials of Example 5a and DPC) of catalyst were placed in a flask equipped with a Vigreux column and distillation bridge. The mixture was melted under a nitrogen blanket and heated to 150 °C with stirring at atmospheric pressure. The mixture was stirred for 30 minutes at 150 °C and for 20 minutes at 180 °C. Subsequently, a vacuum was applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 10 minutes. The mixture was stirred for 30 minutes at 180 °C, for 30 minutes at 190 °C, for 30 minutes at 200 °C, for 10 minutes at 210 °C, for 10 minutes at 220 °C, and for 20 minutes at 240 °C. The pressure was then reduced to < 1 mbar, and condensation was continued for another 60 minutes. The reaction was then stopped. A light yellow, transparent polymer with a Mw of 86,700 g / mol. Example 36: Reaction of Example 5b as UDO component with addition of 0.5 eq. CHDM (according to formula (II), (1)) with DPC as carbonyl source in a molar ratio of 1:1 ((UDO+0.5 eq. CHDM):DPC) in the presence of cat.

[0210] 75.0 g (137.2 mmol, amount of substance calculated from the OH number) of another batch of Example 5b (OH number: 205.3 mg KOH / g), 9.82 g (68.1 mmol) of CHDM, 43.76 g (204.3 mmol) of DPC, and 0.006 g (47 ppm based on the starting materials of Example 5b, CHDM, and DPC) of catalyst were placed in a flask equipped with a Vigreux column and distillation bridge. The mixture was melted under a nitrogen blanket and heated to 150 °C with stirring at atmospheric pressure. The mixture was stirred for 30 minutes at 150 °C and for 25 minutes at 190 °C. Vacuum was then applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 20 minutes. The mixture was stirred for 20 minutes at 190 °C, then the pressure was further reduced to < 1 mbar over 20 minutes and condensed for another 60 minutes. The mixture was then stirred for 4 hours at 220 °C under high vacuum (approx. 0.4 mbar). The reaction was then stopped.A light yellow, transparent polymer with an M was obtained. w of 92,700 g / mol.

[0211] Example 37: Reaction of Example 6 as UDO component with DPC as carbonyl source in a molar ratio of 1:1 (UDO: DPC) in the presence of cat.

[0212] 75.0 g (210.2 mmol, amount calculated from the OH number) of Example 6 (OH number: 314.5 mg KOH / g), 45.03 g (210.2 mmol) of DPC, and 0.006 g (50 ppm based on the starting materials of Example 6 and DPC) of catalyst were placed in a flask fitted with a Vigreux column and distillation bridge. The mixture was melted under a nitrogen blanket and heated to 150 °C at atmospheric pressure with stirring. The mixture was stirred for 10 minutes at 150 °C and for 20 minutes at 180 °C. A vacuum was then applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 10 minutes. The mixture was stirred for 60 minutes at 180 °C, for 10 minutes at 200 °C, and for 10 minutes at 220 °C. The pressure was then reduced to < 1 mbar and condensation continued for another 4 h. After that, the reaction was stopped. A light yellow, transparent polymer with a M w of 52,700 g / mol.

[0213] Example 38: Reaction of Example 7 as UDO component with DPC as carbonyl source in a molar ratio of 1:1 (UDO: DPC) in the presence of cat.

[0214] 75.0 g (126.7 mmol, amount calculated from the OH number) of Example 7 (OH number: 189.5 mg KOH / g), 27.13 g (126.6 mmol) of DPC, and 0.004 g (39 ppm based on the starting materials of Example 7 and DPC) of catalyst were placed in a flask equipped with a Vigreux column and distillation bridge. The mixture was melted under a nitrogen blanket and heated to 150 °C with stirring at atmospheric pressure. The mixture was stirred for 20 minutes at 150 °C and for 20 minutes at 180 °C. A vacuum was then applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 10 minutes. The mixture was stirred for 30 minutes at 180 °C, for 40 minutes at 190 °C, for 20 minutes at 200 °C, for 20 minutes at 210 °C, and for 20 minutes at 220 °C. The pressure was then reduced to <1 mbar (approx. 0.4 mbar), and the mixture was condensed for a further 4 h. The reaction was then stopped. A light yellow, transparent polymer with a M wof 50,300 g / mol.

[0215] Example 39: Reaction of Example 21 as UDO component with DPC as carbonyl source in a molar ratio of 1:1.11 (UDO: DPC) in the presence of cat.

[0216] 150.0 g (257.1 mmol, amount of substance calculated from the OH number) of Example 21 (OH number: 192.3 mg KOH / g), 61.4 g (286.6 mmol) of DPC, and 0.008 g (38 ppm based on the starting materials Example 21 and DPC) of catalyst were placed in a flask fitted with a Vigreux column and distillation bridge. The mixture was melted under a nitrogen blanket and heated to 130 °C at atmospheric pressure with stirring. The mixture was stirred for 50 minutes at 130 °C and for 20 minutes at 180 °C. A vacuum was then applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 15 minutes. The mixture was then gradually heated to 240 °C over 90 minutes. The pressure was then reduced to < 1 mbar, and the mixture was condensed for a further 60 minutes. The reaction was then stopped. A yellow, transparent polymer with an M w of 73,800 g / mol.

[0217] Example 40: Reaction of Example 22 as UDO component with DPC as carbonyl source in a molar ratio of 1:1.03 (UDO: DPC) in the presence of cat.

[0218] 75.0 g (141 mmol, amount of substance calculated from the OH number) of Example 22 (OH number: 210.9 mg KOH / g), 31.0 g (144.7 mmol) of DPC and 0.004 g (38 ppm based on the starting materials Example 22 and DPC) of catalyst were placed in a flask fitted with a Vigreux column and distillation bridge. The mixture was melted under a nitrogen blanket and heated to 130 °C at atmospheric pressure with stirring. The mixture was stirred for 5 minutes at 130 °C, 5 minutes at 140 °C and then for 20 minutes at 180 °C. A vacuum was then applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 5 minutes. The mixture was then heated gradually to 240 °C over 105 minutes. The pressure was then reduced to < 1 mbar and the mixture was condensed for a further 90 minutes. After this time, the reaction was stopped. A yellow, transparent polymer with a M w of 127,900 g / mol.

[0219] Example 41: Reaction of Example 24 as UDO component with DPC as carbonyl source in a molar ratio of 1:1.10 (UDO:DPC) in the presence of cat. 75.0 g (132.9 mmol, amount of substance calculated from the OH number) of Example 24 (OH number: 198.8 mg KOH / g), 31.3 g (146.1 mmol) of DPC and 0.004 g (38 ppm based on the starting materials Example 24 and DPC) of cat were placed in a flask fitted with a Vigreux column and distillation bridge. The mixture was melted under a nitrogen blanket and heated to 130 °C at atmospheric pressure with stirring. The mixture was stirred for 20 minutes at 130 °C and for 30 minutes at 180 °C. Vacuum was then applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over a period of 30 minutes. The mixture was then gradually heated to 240 °C over a period of 60 minutes. The pressure was then increased to

[0220] < 1 mbar and the mixture was condensed for a further 60 minutes. The reaction was then stopped. A yellow, transparent polymer with an M w of 79,600 g / moL

[0221] Example 42: Reaction of Example 25 as UDO component with DPC as carbonyl source in a molar ratio of 1:1.14 (UDO:DPC) in the presence of cat.

[0222] 75.0 g (138.2 mmol, amount of substance calculated from the OH number) of Example 25 (OH number: 206.8 mg KOH / g), 33.9 g (158.2 mmol) of DPC, and 0.004 g (37 ppm based on the starting materials of Example 25 and DPC) of catalyst were placed in a flask fitted with a Vigreux column and distillation bridge. The mixture was melted under a nitrogen blanket and heated to 130 °C at atmospheric pressure with stirring. The mixture was stirred for 15 minutes at 130 °C and for 20 minutes at 180 °C. A vacuum was then applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 10 minutes. The mixture was then gradually heated to 240 °C over 70 minutes. The pressure was then reduced to

[0223] < 1 mbar and the mixture was condensed for a further 60 minutes. The reaction was then stopped. A yellow, transparent polymer with an M w of 43,300 g / moL

[0224] Example 43: Reaction of Example 32 as UDO component with DPC as carbonyl source in a molar ratio of 1:1 (UDO: DPC) in the presence of cat.

[0225] 150.0 g (184.1 mmol, amount calculated from the OH number) of Example 32 (OH number: 137.7 mg KOH / g), 39.43 g (184.1 mmol) of DPC, and 0.007 g (37 ppm based on the starting materials Example 32 and DPC) of catalyst were placed in a flask fitted with a Vigreux column and distillation bridge. The mixture was melted under a nitrogen blanket and heated to 160 °C at atmospheric pressure with stirring. The mixture was stirred for 20 minutes at 160 °C and for 20 minutes at 190 °C. A vacuum was then applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 30 minutes, and the bath temperature was increased to 220 °C. The mixture was stirred for 30 minutes at 220 °C. The pressure was then reduced to < 1 mbar and the mixture was condensed for a further 2 h. The reaction was then stopped. A light yellow, transparent polymer with a M wof 68,300 g / mol. Example 44: Reaction of Example 33 as UDO component with DPC as carbonyl source in a molar ratio of 1:1 (UDO:DPC) in the presence of cat.

[0226] 75.0 g (79.1 mmol, amount of substance calculated from the OH number) of Example 32 (OH number: 118.3 mg KOH / g), 16.94 g (79.1 mmol) of DPC, and 0.002 g (22 ppm based on the starting materials of Example 33 and DPC) of catalyst were placed in a flask fitted with a Vigreux column and distillation bridge. The mixture was melted under a nitrogen blanket and heated to 160 °C at atmospheric pressure with stirring. The mixture was stirred for 10 minutes at 160 °C and for 20 minutes at 190 °C. A vacuum was then applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 10 minutes. The mixture was stirred for 60 minutes at 190 °C and for 10 minutes at 220 °C. The pressure was then reduced to < 1 mbar within 10 minutes, and the mixture was condensed for a further 60 minutes. After that, the reaction was stopped. A light yellow, transparent polymer with a M w of 93,300 g / mol.

[0227] Table 3: Comparison of the results of examples 34 to 44. *A first impression was gained by bending the solidified melt by hand. The material is called "ductile" if it did not break during this process. Otherwise, it is called "brittle."

Claims

1. Urethanediol prepolymer having a structure of formula (I) where each R 1 in formula (I) each independently represents a group comprising at least one cycle and having 6 to 18 carbon atoms, which is a cycloaliphatic or heterocycloaliphatic group, and wherein each R 2 of formula (I) each independently represents a group comprising at least one cycle and having 6 to 18 carbon atoms, which is a cycloaliphatic, aromatic, heterocycloaliphatic or heterocyclic-aromatic group, where m is the arithmetic mean of the repeating units and is a number > 1.

7.

2. Urethanediol prepolymer according to claim 1, 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 200 to 10,000 g / mol.

3. Urethanediol prepolymer according to claim 1 or 2, characterized in that R 1 in formula (I) is represented by formula (1), formula (2), formula (3), formula (4), formula (5) and / or formula (6) wherein the positions marked with an asterisk "*" in formulas (1), (2), (3), (4), (5), and (6) are the positions at which the oxygen atoms shown in formula (I) are located.

4. Urethanediol prepolymer according to any one of the preceding claims, characterized in that R 2 in formula (I) is represented by one of the formulas (7), (8), (9), (10), (11), (12), (13), (14) and / or (15) (15), where the positions marked with an asterisk in formulas (7) to (15) are the positions at which the nitrogen atoms shown in formula (III) are located, and where each R 3in formula (7) each 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 (9) independently represents a methyl or ethyl group and p represents 0, 1 or 2, where each R 3 in formula (14) 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 (15) independently represents a methyl or ethyl group and p represents 0, 1, or 2 and d each independently represents 0 or 1.

5. Urethanediol prepolymer according to one of the preceding claims, characterized in that the glass transition temperature T g of the urethanediol prepolymer is > 2°C, with the glass transition temperature being determined by differential scanning calorimetry.

6. Urethanediol prepolymer according to one of claims 1 to 4, characterized in that the glass transition temperature T g of the urethanediol prepolymer is > 25 °C, with the glass transition temperature being determined by differential scanning calorimetry.

7. A urethane diol prepolymer according to any one of the preceding claims, wherein the urethane diol prepolymer is prepared by a process according to any one of claims 10 to 13.

8. Urethanediol prepolymer according to one of the preceding claims, wherein the urethanediol prepolymer has an OH number, determined by titration in accordance with DIN EN ISO 4629-2, between 10 and 1000 mg KOH / g, where "in accordance" means that pyridine is used instead of the base JV-methyl-2-pyrrolidone.

9. Urethanediol prepolymer according to any one of the preceding claims, wherein R 1 corresponds to formula (1) or (2) and R 2 corresponds to formula (7) or (14).

10. A process for producing a urethanediol prepolymer, comprising the process step (i) Reaction of one or more diols of formula (II) HO - R 1 - OH (II), where R 1 in formula (II) represents a group comprising at least one cycle and having 6 to 18 carbon atoms, which is a cycloaliphatic or heterocycloaliphatic group, with one or more diisocyanates of formula (III) OCN — — NCO 111), where R 2 in the formula (III) represents a group comprising at least one cycle and having 6 to 18 carbon atoms, which is a cycloaliphatic, aromatic, heterocycloaliphatic or heterocyclic-aromatic group, to a urethanediol prepolymer, characterized in that in process step (i) the molar ratio of all diols used to all diisocyanates used is 3.7: 1.0 to 1.1: 1.

0.

11. The process according to claim 10, characterized in that in a further process step at least a portion of the unreacted diol of formula (II) is removed from the urethanediol prepolymer.

12. The method according to claim 10 or 11, characterized in that R 1 in formula (II) is represented by formula (1), formula (2), formula (3), formula (4), formula (5) and / or formula (6) where the positions marked with the asterisk "*" in formulas (1), (2), (3), (4), (5) and (6) are the positions at which the OH groups shown in formula (II) are located.

13. The method according to any one of claims 10 to 12, characterized in that the structure R 2 in formula (III) is represented by one of the formulas (7), (8), (9), (10), (11), (12), (13), (14) and / or (15) (15), wherein the positions marked with an asterisk in formulas (7) to (15) are the positions at which the nitrogen atoms of the isocyanate groups shown in formula (III) are located, and wherein each R 3 in formula (7) 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 (9) independently represents a methyl or ethyl group and p represents 0, 1 or 2 and wherein each R 3 in formula (14) 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 (15) independently represents a methyl or ethyl group and p represents 0, 1, or 2 and d each independently represents 0 or 1.

14. Use of a urethane diol prepolymer according to any one of claims 1 to 9 for the preparation of a polymer.

15. Use of a urethane diol prepolymer according to claim 14, wherein the polymer is a poly(urethane-co-carbonate).

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