Thermoplastic poly(urethane- co-carbonate)

Abstract

The invention relates to a thermoplastic poly(urethane-co-carbonate) and to a method for producing same. The poly(urethane-co-carbonate) has a molar weight average of at least 40.000 g / mol and a defined ratio of carbonate groups and urethane groups.

Description

[0001] THERMOPLASTIC POLY(URETHANE CO-CARBONATE)

[0002] The present invention relates to a thermoplastic poly-(urethane-co-carbonate) and a process for its preparation.

[0003] Aromatic polycarbonates are known for their excellent properties in terms of mechanical and optical performance, heat resistance, and weathering stability. However, the presence of aromatic groups means that these properties are subject to improvements in transmission, birefringence, and yellowing. In contrast, aliphatic polycarbonates exhibit improved properties in these areas, as well as in chemical resistance, but they generally have low glass transition temperatures and, consequently, lower heat resistance. Therefore, efforts are being made to provide aliphatic polycarbonates with an overall improved property profile.

[0004] In EP 2 883 898 A1, an aliphatic polycarbonate is blended with a polyurethane. The mechanical properties of the aliphatic polycarbonate were improved by forming an IPN (interpenetrating polymer network). The aliphatic polycarbonate is a polypropylene carbonate or polyethylene carbonate. It thus contains linear aliphatic structures, which generally result in low glass transition temperatures (approximately 25-45 °C). Furthermore, the examples in this document exclusively use 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 with 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 thermoplastic polycarbonate using (or co-using) aliphatic starting materials, which has glass transition temperatures of at least 90 °C. Through the (co-using) use of aliphatic starting materials, the thermoplastic polycarbonate should have good optical properties (in particular transparency). At the same time, the thermoplastic polycarbonate should preferably also have high heat resistance (despite the use of aliphatic structural components). Likewise preferably, the thermoplastic polycarbonate should be processable using the plasticizing methods commonly used for aromatic polycarbonate (e.g. injection molding, (co)extrusion, blow molding, deep drawing).For this purpose, it is particularly advantageous if the thermoplastic polycarbonate is amorphous. Likewise, the thermoplastic polycarbonate should preferably have good mechanical properties, for example, properties comparable to those of aromatic polycarbonate. It is particularly preferred that the thermoplastic polycarbonate exhibit at least a ductile fracture at room temperature.

[0008] At least one of the stated objects, preferably all of the stated objects, has been achieved by the present invention.

[0009] It has surprisingly been found that a poly(urethane-co-carbonate) with a minimum molar mass, which has at least one specific structure of formula (I) and at least one specific structure of formula (II) and has a defined molar proportion of carbonate groups based on the sum of the carbonate and urethane groups, has a glass transition temperature of at least 90°C. The structure of formula (I) can be obtained, for example, by using an aliphatic primary diol which has at least one cycle. The structure of formula (II) can also be obtained by using a secondary or tertiary diisocyanate which has at least one cycle. It has been 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 90°C can be achieved.The ratio of carbonate to urethane groups can be adjusted, for example, by the ratio of the diol(s) used to the diisocyanate(s) used. Furthermore, it can be influenced by the targeted addition or removal of diols prior to reaction of the prepolymer with a carbonyl source. Likewise, different copolymers with different ratios of carbonate to urethane groups can be blended in a blend to specifically adjust the ratio. The thermoplastic poly(urethane-co-carbonates) according to the invention exhibit correspondingly good heat resistance. A glass transition temperature in this range enables 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) can be used, in particular 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" according to the invention preferably serves to differentiate between thermosetting and / or elastomeric polymers. Such thermosetting and / or elastomeric polymers have physical crosslinking of the individual polymer chains, which means that deformation (which goes beyond the elastic range) is irreversible. Such polymers cannot be deformed / shaped using common plasticizing processes.

[0010] The thermoplastic poly(urethane-co-carbonates) according to the invention are amorphous. This, among other things, gives them good optical properties. In particular, the poly(urethane-co-carbonates) according to the invention are transparent. The term "transparent" in the context of the present invention is preferably to be understood as meaning that injection-molded sheets have a light transmission in the VIS range of the spectrum (380 to 780 nm) of at least 20%, preferably at least 50%, particularly preferably at least 70%, likewise preferably at least 80% (transmission factor TVIS), determined according to DIN ISO 13468-2:2006 (D65, 10°, layer thickness of the sample sheet: 4 mm). Likewise preferably, these injection-molded sheets simultaneously have a haze of less than 30%, preferably less than 20%, very particularly preferably less than 10%, and equally particularly preferably less than 7%, determined according to ASTM D1 003:2013. In particular, this refers to injection-molded sheets that exhibit visual transparency, i.e.depict the background.

[0011] Likewise, the thermoplastic poly(urethane-co-carbonates) 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-carbonates) according to the invention are amorphous, they exhibit, in particular, no shrinkage. 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 if an amorphous polymer is used.Although 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.

[0012] Furthermore, the thermoplastic poly(urethane-co-carbonates) according to the invention exhibit good mechanical properties, for example, at least a ductile fracture at room temperature. Thus, the thermoplastic poly(urethane-co-carbonates) according to the invention exhibit, in particular, a good property profile that is comparable, preferably better, than that of conventional aromatic polycarbonates (e.g., based on bisphenol A). In particular, the thermoplastic poly(urethane-co-carbonates) according to the invention exhibit, in addition to their good mechanical properties, good chemical resistance (particularly 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, so that the common disadvantages of the presence of aromatic groups in the polymer can be reduced, in particular avoided. According to the invention, a thermoplastic poly(urethane-co-carbonate) is provided, comprising structures of the formulas (I) and (II), wherein. in which each R 1 in formula (I) each independently represents an aliphatic group having 6 to 18 carbon atoms, which has at least one cycle and this cycle may optionally contain at least one heteroatom, and where each R 2in 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 formulas (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 formulas (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 less than 58 mol% to greater than 0 mol%, preferably up to greater than 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, 13C-NMR spectroscopy and that the thermoplastic poly(urethane-co-carbonate) has a weight-average molecular weight of at least 40,000 g / mol. According to the invention, the term “poly(urethane-co-carbonate)” is used to describe a polymer which has the features according to the invention. This polymer 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 which differ from the structures of the 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. The poly(urethane-co-carbonate) according to the invention therefore preferably has no ether groups. The poly(urethane-co-carbonate) according to the invention particularly preferably has no 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 does not contain any 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.

[0013] Likewise, 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.

[0014] It is also 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.

[0015] 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 formed structures constitute the essential part of the polymer chain of the poly(urethane-co-carbonate). For example, by linking at least some of the structures (I) with at least one further structure of the formula (I) directly to one another, a structure of the formula (IA) can be formed:

[0016] R 1 for 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).

[0017] 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:

[0018] 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.

[0019] 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).

[0020] The poly(urethane-co-carbonate) according to the invention is preferably obtained by the process according to the invention explained in more detail below. In this process, diols are first reacted with diisocyanates. The resulting prepolymer is then reacted with a carbonate 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 polymer chain of the poly(urethane-co-carbonate).This particularly preferably means that the poly(urethane-co-carbonate) consists 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.

[0021] 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 be introduced, for example, 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.

[0022] According to the invention, the poly(urethane-co-carbonate) comprises structures of the formula (I)

[0023] (I), where each R 1 in the formula (I) each independently represents an aliphatic group having 6 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 6 to 18 carbon atoms can also be part of two cycles.

[0024] Preferably R 1 for a Ce to Cis-cycloalkylene group. "Cycloalkylene" preferably means a bridging cycloalkane structure from which two hydrogen atoms have been removed from different carbon atoms. It is not excluded that the bonding to the CFE groups 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 1 at least one cycle). The two carbon atoms from which the two hydrogen atoms have been removed can be any, i.e., any part of the cycle or of the linear alkylene group, if present. Furthermore, the cycloalkene 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.

[0025] 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.

[0026] The R is preferred 1in formula (I), (IA), (IIA) (or also in formula (III) 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 (III) are located, respectively.

[0027] 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 connection of the structure of formulas (II) and (12) into the chain of the poly(urethane-co-carbonate).

[0028] 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 (li): where each R 6in formula (li) represents an aliphatic alkylene group having 4 to 20, preferably 5 to 18, particularly preferably 6 to 16 carbon atoms, which may be linear, branched or 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 (li) via a CH2 group at least on one side, preferably on both sides, and wherein the wavy lines in formula (li) each represent the connection of the structure of formula (li) into the chain of the poly(urethane-co-carbonate). These structures of formula (li) can be at least partially directly bonded to another structure of formula (li) to form a carbonate group, or else at least partially to a structure of formula (I). Likewise, the structures of formula (li) 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 (li) 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 (Ii). It is apparent to those skilled in the art that structure (Ii) cannot correspond to formula (I).

[0029] Particularly preferably, the poly(urethane-co-carbonate) according to the invention comprises, in addition to the

[0030] Structures of formula (I) also at least one further structure of formulas (lia) to (lid) where the wavy lines in formulas (lia) to (lid) each represent the connection of the structure of the formulas into the chain of the poly(urethane-co-carbonate).

[0031] The amount of the further structure of formula (li) or of the preferred structures (Iia) to (Id) in the poly(urethane-co-carbonate) according to the invention is preferably chosen such that the resulting glass transition temperature of the poly(urethane-co-carbonate) remains above 90°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 formula (li) or of the preferred structures (Iia) to (Iid) based on the sum of the structures (Ii) (or (Iia) to (Iid)) and the structures (I). It is obvious 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 (Ii).However, if at least one structure of formula (Ii) or a preferred structure of formula (Iia) to (Iid) is necessarily present, the term "at most" in this context means that more than 0 mol% is present.

[0032] However, the poly(urethane-co-carbonate) according to the invention preferably does not contain any structures of the formula (Ii) in which R 6 represents a -CH2CH2CH2CH2- group.

[0033] 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) in each case 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.

[0034] 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.

[0035] Particularly preferred is the structure R 2 in formula (II), (IIA) (or formula (III) shown later) 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 (II), (IIA) and formula (III) 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.

[0036] 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. 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

[0037] - a linear alkylene group with 4 to 12 carbon atoms,

[0038] - 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

[0039] - 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 present in a statistically distributed manner 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 any structure of formula (Ili).

[0040] Very particularly preferably, the poly(urethane-co-carbonate) according to the invention comprises, in addition to the structures of formula (II), also at least one further structure of formula (IIa) to (IIh): 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 (IIg) 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 (IIa) to (IIh) are the positions at which the nitrogen atoms shown in formula (II), (IIA) or formula (III) are located.

[0041] The amount of the further structure of formula (IIi) or of the preferred structures (IIa) to (IIh) 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 above 90°C. In addition, ductile fracture should be present at least at room temperature. Furthermore, the amount of the further structure of formula (IIi) must be adjusted if necessary to maintain the preferred aromatic content of the resulting poly(urethane-co-carbonate), as preferably defined according to the invention.The poly(urethane-co-carbonate) according to the invention particularly preferably contains at most 95 mol%, particularly preferably at most 93 mol%, likewise preferably at most 90 mol%, likewise particularly preferably at most 80 mol%, likewise preferably at most 70 mol%, likewise preferably at most 60 mol%, likewise preferably at most 50 mol%, likewise preferably at most 40 mol%, likewise preferably at most 30 mol%, likewise preferably at most 20 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 obvious 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 (IIi).However, if at least one structure of formula (Ili) or a preferred structure of formula (Ilia) to (Ilih) is necessarily present, the term "at most" in this context means that more than 0 mol% is present.

[0042] Particularly preferably, the poly(urethane-co-carbonate) according to the invention comprises structures of the formula (II) and / or (II) 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.

[0043] According to the invention, the poly(urethane-co-carbonate) has less than 58 mol% to greater than 0 mol%, preferably less than 58 mol% to greater than 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 13C-NMR spectroscopy. 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 90°C. In addition, the polymers thereby exhibit ductile fracture at least at room temperature. The poly(urethane-co-carbonate) preferably has less than 57 mol% to greater than 5 mol%, more preferably less than 56 mol% to greater than 10 mol%, furthermore preferably less than 53 mol% to greater than 17 mol%, likewise preferably less than 50 mol% to greater than 18 mol%, and most preferably less than 48 mol% to more than 20 mol% carbonate groups, based on the sum of the carbonate and urethane groups in the poly(urethane-co-carbonate).

[0044] The determination of the carbonate and urethane groups is carried out via 13 C NMR spectroscopy.

[0045] 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% ratio of the carbon atoms, the area under the signals is integrated and compared to each other.This is a process known to those skilled in the art.

[0046] Furthermore, the poly(urethane-co-carbonate) according to the invention 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 200,000 g / mol, particularly preferably from 50,000 g / mol to 150,000 g / mol, especially preferably from 52,000 g / mol to 100,000 g / mol, and very particularly preferably from 55,000 g / mol to 90,000 g / mol. It has been found that, within this defined molar mass range, the poly(urethane-co-carbonate) according to the invention has good properties, in particular good thermoplasticity. 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 while still maintaining good mechanical properties, particularly ductility. This preferably means that, if no aromatic groups are present in the poly(urethane-co-carbonate) according to the invention, the weight-average molecular weight is from 40,000 g / mol to 200,000 g / mol, particularly preferably from 50,000 g / mol to 150,000 g / mol, especially preferably from 52,000 g / mol to 100,000 g / mol, and very particularly preferably from 55,000 g / mol to 90,000 g / mol.Likewise preferably, this means that if the poly(urethane-co-carbonate) according to the invention has aromatic groups, it has a weight-average molecular mass of 40,000 g / mol to 200,000 g / mol, particularly preferably of 41,000 g / mol to 150,000 g / mol, especially preferably of 42,000 g / mol to 100,000 g / mol and very particularly preferably of 43,000 g / mol to 90,000 g / mol.

[0047] This weight average molecular weight (M w) and / or all other molecular weights of the invention, unless otherwise stated, were determined by gel permeation chromatography in tetrahydrofuran using a polystyrene standard (preferably based on DIN 55672-1:2007-08 using a polystyrene calibration). Calibration was performed using narrowly distributed polystyrene standards (e.g., ReadyCal Kit Polystyrene low, nominal Mp 266 66,000 Da). The general method is defined by Currenta GmbH & Co. OHG under AM 2011-0623701-09D, which can be requested from Currenta at any time. Tetrahydrofuran (THF) was used as the eluent. The GPC may comprise one or more commercially available GPC columns (e.g. SDV columns) connected in series for size exclusion chromatography, which are selected so that a sufficient separation of the molecular weights of polymers, in particular of the polymers according to the invention with weight-average molecular weights M wfrom 2,000 to 100,000 g / mol. Detection can be achieved via ultraviolet radiation (UV) and / or refractive index.

[0048] It is preferred that the thermoplastic poly(urethane-co-carbonate) according to the invention contains at most 60 mol%, preferably at most 58 mol%, particularly preferably at most 55 mol%, likewise preferably at most 50 mol%, likewise preferably at most 45 mol%, likewise preferably at most 40 mol%, likewise preferably at most 35 mol%, likewise preferably at most 30 mol%, likewise preferably at most 25 mol%, likewise preferably at most 20 mol%, likewise preferably at most 15 mol%, likewise preferably at most 10 mol% and very particularly preferably at most 5 mol% of aromatic groups, this amount being based on the total amount of aliphatic and aromatic groups. It is clear that the formulation “at most” covers the range from 0 mol% to the stated mol%. Most preferably, the thermoplastic poly(urethane-co-carbonate) according to the invention is aliphatic.However, as already explained above, this does not exclude traces of aromatic compounds that are present in the polymer due to impurities and / or end groups.

[0049] It has proven advantageous to limit the amount of aromatic groups in the poly(urethane-co-carbonate) according to the invention in order to minimize the disadvantages associated with the presence of aromatic groups (see above). Aromatic groups can be present in the polymer according to the invention, in particular through the presence of additional structures of formula (Ii) and / or (Iii). The proportion of aromatic groups can be determined in a manner known to the person skilled in the art. 'H NMR spectroscopy is particularly suitable for this purpose.

[0050] It is preferred that the thermoplastic poly(urethane-co-carbonate) according to the invention comprises the structural formula (III) where each R 1has the meanings given for formula (I), where the group -CFt-R'-CFfc- enclosed by the round brackets also partly independently of one another represents R 6 provided that at least part of the structures is -CFF-R'-CFF-, and R 6 has the meanings given for formula (li), where if R 6 has at least one cycle, is not bound into the structure (III) via a CH: 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 7has the meanings given for formula (IIi), m is the arithmetic mean of the repeating units and is a number between 1.7 and 5.0 and the wavy lines represent the connection of the structure of formula (III) into the chain of the poly(urethane-co-carbonate).

[0051] 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 already described above 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.

[0052] In particular, it is preferred that in formula (III) the larger proportion of the sum of the structures -CH2-R'-CH2- and R 6 the structure -CH2-R'-CH2-. This means that the larger proportion of the groups -CH2-R'-CH2- and R 6 is bonded into the polymer chain via secondary carbon atoms. It is also preferred, in particular at the same time, that in formula (III) the larger proportion of the sum of the groups R 2 and R 7 Group R 2 This means that the majority of groups are bonded into the polymer chain via two secondary and / or tertiary carbon atoms.

[0053] It will be clear to the person skilled in the art how the structure of formula (III) results from the structures of formula (I), (II), (Ii) and / or (Ii). Particularly preferably, formula (III) is represented by the following formula (IiI), where each R 1 , R 2and m has the meanings given for formula (III). The skilled person will be aware that formula (III) may also be statistically interrupted by the presence of formulas (Ii) and / or (Ili).

[0054] Furthermore, it is preferred that the thermoplastic poly(urethane-co-carbonate) according to the invention comprises, in addition to the structure of formula (III) or (III), repeating units of formula (IV) 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 6has 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 preferably a number that arises statistically when the poly(urethane-co-carbonate) comprises 2 to 35 wt. %, preferably 3 to 30 wt. %, of the groups of formula (IV). The skilled person is able to determine the proportion of groups of formula (IV) using methods customary to him, such as, for example, NMR spectroscopy. The method may also depend on the type of monomers used. The thermoplastic poly(urethane-co-carbonate) according to the invention most preferably has a structure of formula (V). where each R 1 has the meanings given for formula (I), where the group enclosed by the round brackets -CEL-R'-CEL- also partly independently of one another represents R 6provided that at least part of the structures is -CEE-R'-CEE-, 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 7 has 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 1.7 and 5.0 and x or 1-x is the relative ratio of the respective repeating units to one another.

[0055] 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 (V) 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 (V). This then makes r greater than 1.

[0056] It is obvious to the person skilled in the art that x must be less than 1.

[0057] It will be apparent to the skilled person that the end groups in formula (V) do not necessarily have to be methyl groups, but can merely represent a potential end of the chain of formula (V) or be a further point of attachment to other groups. - TI -

[0058] It is preferred that the thermoplastic poly(urethane-co-carbonate) has a glass transition temperature above 90 °C, preferably above 91 °C, particularly preferably above 95 °C. The glass transition temperature (Tg) can preferably be determined by means of differential scanning calorimetry (DSC) according to the standard DIN EN ISO 11357-1:2009-10 and ISO 11357-2:2013-05. In particular, a heating rate of 20 K / min under nitrogen is used, and the T g is determined as the inflection point in the second heating process. 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).

[0059] The thermoplastic poly(urethane-co-carbonate) 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 containing the thermoplastic poly(urethane-co-carbonate) according to the invention are further subject matter 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., hydrolysis and heat-aging stabilizers and transesterification inhibitors), flow promoters, phase compatibilizers, dyes and pigments, impact modifiers, and fillers and reinforcing materials.

[0060] The molded articles 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.

[0061] In a further aspect of the present invention, a process for producing a thermoplastic poly(urethane-co-carbonate) is provided, comprising the process steps

[0062] (i) Reaction of at least one aliphatic diol of formula (la) ( / T la \), where each R in the formula (la) independently of one another represents an aliphatic group having 6 to 18 carbon atoms, which has at least one cycle and which cycle may optionally contain at least one heteroatom, with at least one aliphatic diisocyanate of the formula (IIa)

[0063] OCN — R 2 - NCO7

[0064] (Ila), where R in the formula (Ila) represents a bridging aliphatic structure having 6 to 18 carbon atoms, where this bridging structure has at least one cycle and where this cycle may optionally contain at least one heteroatom and where the bridging structure is bonded to the nitrogen atoms shown in structure (Ila) via a secondary or tertiary carbon atom, to a prepolymer and

[0065] (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 3.7: 1 to 1.3: 1, preferably 3.6: 1 to 1.4: 1, likewise preferably 3.5: 1 to 1.5: 1, particularly preferably 2.5: 1 to 1.8: 1.

[0066] 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), (IV), and (V).

[0067] 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. This is preferably the thermoplastic poly(urethane-co-carbonate) according to the invention.

[0068] The molar ratio of all diols used, in particular the aliphatic diol of formula (Ia), to all diisocyanates used, in particular the 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).

[0069] In process step (i), at least one aliphatic diol of formula (Ia) is used. It is clear that only this aliphatic diol of formula (Ia) can be used as the sole diol. R 1 in formula (la) preferably has the above-mentioned meanings of R 1 to formula (I). In particular, it is evident that if R 1 has more than one cycle, one or more of the 6 to 18 carbon atoms can also be part of two cycles. R is particularly preferably 1in formula (Ia) represents a Ce-Cis-cycloalkylene group as described above. 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 stem in formulas (1) and (2) are the positions at which the CFF groups shown in formula (1a) are located, respectively.

[0070] In addition to the aliphatic diol of formula (Ia), one or more further diols can also be used in process step (i). It is preferred that the one or more further diols be used in process step (i) at a maximum of 75 mol%, particularly preferably at a maximum of 60 mol%, likewise preferably at a maximum of 40 mol%, likewise particularly preferably at a maximum of 25 mol%, likewise preferably at a maximum of 10 mol%, and very particularly preferably at a maximum of 5 mol%, based on all diols used.

[0071] The one or more further diols in process step (i) are preferably at least one diol of the formula (X)

[0072] HO-R 6 -OH (X), where each R 6 has the meanings given for formula (li). However, it is preferred that no diol containing an ether group is used in process step (i) of the process according to the invention. It is also preferred that no diol containing an ester group is 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 diols can also be derived by the person skilled in the art from the abovementioned preferences for formula (li).

[0073] In this context, it is understood that the invention frequently refers to "at least" one compound such as a diol or a diisocyanate and 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.

[0074] In process step (i), at least one aliphatic diisocyanate of the formula (IIa) is further used. It is clear that only this aliphatic diisocyanate of the formula (IIa) can be used as the sole diisocyanate. Here, 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), where the positions marked with the stem “*” 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.

[0075] Particular preference is given in process step (i) of the process according to the invention to aliphatic diols of the formula (Ia), where R 1 which has formula (1) and / or (2), and structures of formula (Ila) 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-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.

[0076] In addition to the aliphatic diisocyanate of the formula (IIa), 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 up to a maximum of 95 mol%, particularly preferably a maximum of 93 mol%, likewise preferably a maximum of 90 mol%, likewise particularly preferably a maximum of 80 mol%, likewise preferably a maximum of 70 mol%, likewise preferably a maximum of 60 mol%, likewise preferably a maximum of 50 mol%, likewise preferably a maximum of 40 mol%, likewise preferably a maximum of 30 mol%, likewise preferably a maximum of 20 mol%, likewise preferably a maximum of 10 mol%, and very particularly preferably a maximum of 5 mol%, based on the at least one diisocyanate of the formula (IIa).

[0077] The one or more further diisocyanates in process step (i) are preferably at least one diisocyanate of the formula (Xi)

[0078] OCN-R 7 -NCO (Xi), where each R 7 has the meanings given for formula (IIi). Particularly preferred diisocyanates can also be derived by the person skilled in the art from the above-mentioned preferences for formula (IIi).

[0079] In process step (i) according to the invention, a prepolymer is prepared. The prepolymer preferably has a M n in the range from 200 to 3000 g / mol, particularly preferably from 220 to 2000 g / mol, most preferably from 230 to 1660 g / mol. This number-average molecular weight M nby gel permeation chromatography. The method already explained above as preferred according to the invention is very particularly preferably used for this purpose. A preferred prepolymer according to the invention, which is used for the preparation of thermoplastic poly(urethane-co-carbonate) according to the invention, is a urethanediol prepolymer with a build-up factor as defined below, having a structure of the formula (XX) where each R 1 in the formula (XX) 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 (XX) each independently represents a group comprising at least one cycle and having 6 to 18 carbon atoms, which is a cycloaliphatic or heterocycloaliphatic group, wherein the bonding of the structure R2 to the nitrogen atoms shown in structure (XX) occurs via a secondary or a tertiary carbon atom, wherein m is the arithmetic mean of the repeating units and is a number between 1.7 and 5.0.

[0080] A particularly preferred prepolymer according to the invention is one in which R 1 is represented by where the positions marked with an asterisk in formulas (1a) and (2a) are the positions at which the oxygen atoms shown in formula (XX) are located, and R 2 is represented by where the positions marked with the star in formula (3) are the positions at which the nitrogen atoms shown in formula (XX) 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.

[0081] 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 from 90°C to 200°C, preferably 100°C to 180°C, more preferably 110°C to 150°C, and most preferably 115°C to 145°C. Due to the exothermic nature of the reaction, the reaction mixture may at least temporarily have a temperature of 100°C to 200°C, preferably 150°C to 195°C, and more preferably 170°C to 190°C. The reaction is exothermic, so the reaction can also be counter-cooled.If the reaction of process step (i) is already carried out in the presence of the at least one diaryl carbonate, it is preferable that the temperature is not too high. This can initially minimize the reaction of the diaryl carbonate according to process step (ii). The upper temperature limit in this case is preferably between 90 °C and 180 °C.

[0082] Process step (i) can be carried out under nitrogen at atmospheric pressure. However, it can also be carried out under reduced or elevated pressure.

[0083] 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.

[0084] 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 is used as the diol). Aromatic hydrocarbons, particularly chlorobenzene, are preferably used for this purpose. It is preferred that no solvent be present in process step (i). This eliminates the need for an additional solvent removal step.

[0085] 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 Bachmann 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.

[0086] As catalysts, preference is given to using (A) urea, derivatives of urea and / or (B) the abovementioned amines and amino ethers, characterized in that the amines and amino ethers contain a functional group which reacts chemically with the isocyanate. Preferably, the functional group is a hydroxyl group, a primary or secondary amino group. These particularly preferred catalysts have the advantage of having 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-

[0087] (dimethylamino)ethoxy]ethyl]-N-methyl-1,3-propanediamine and 3-

[0088] Dimethylaminopropylamine and its derivatives and comparable molecules in which the dimethylamino group is replaced by a pyrrolidine group according to WO 2022 / 112157 A1.

[0089] The use of monobutyltin oxide and / or dibutyltin oxide as catalyst in process step (i) is particularly preferred.

[0090] 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, and very particularly preferably 50 to 170 ppm, based on the mass of all diisocyanates used. For the purposes of the present invention, ppb and ppm are parts by weight, unless otherwise stated.

[0091] 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 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.

[0092] 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.

[0093] According to the invention, the use of both a cycloaliphatic diol and a cycloaliphatic diisocyanate results in a polymer having a high glass transition temperature of at least 90°C. Furthermore, it has proven particularly advantageous to at least partially remove the (unreacted) aliphatic diol (of formula (Ia) and optionally of formula (X)) 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. 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 (IV) shown above can be influenced.For example, the thermoplastic poly(urethane-co-carbonate) according to the invention generally contains repeating units of the formula (IV) if, at the beginning of process step (ii), previously unreacted diols are still present in the prepolymer.

[0094] The unreacted aliphatic diol of formula (Ia) (and optionally of formula (X)) 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).

[0095] 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).

[0096] According to the invention, it has been found that a sufficiently high molecular weight increase is achieved using a diaryl carbonate, in particular diphenyl carbonate. Experiments conducted using otherwise comparable parameters, but with dimethyl carbonate instead of diphenyl carbonate, show that such a dialkyl carbonate does not produce a sufficient molecular weight increase to obtain a poly(urethane-co-carbonate) according to the present invention.

[0097] 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, optionally, from unreacted diol and / or further diol. The OH groups of the prepolymer are preferably determined by determining the OH number. However, they can also be calculated theoretically.

[0098] 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 (see above, 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.

[0099] 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, increasing the temperature, and applying a vacuum.

[0100] Process step (ii) is preferably carried out at a temperature of 180°C to 260°C, more preferably 215°C to 255°C, and most preferably 220°C to 250°C. The specified temperature is preferably the final temperature. According to the invention, the final temperature can be achieved by gradually increasing the temperature.

[0101] The reaction in process step (ii) generally produces a condensation product. To shift the reaction equilibrium, 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, preferably 200 mbar to 0.01 mbar, particularly preferably 200 mbar to 0.1 mbar. In particular, it is preferred that the vacuum be reduced gradually. Very particularly preferably, the vacuum in the final stage is 10 mbar to 0.01 mbar.

[0102] 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.

[0103] 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,

[0104] Tetraphenylphosphonium fluoride, tetraphenylphosphonium tetraphenylboranate,

[0105] Dimethyldiphenylammonium hydroxide, tetraethylammonium hydroxide,

[0106] Cethyltrimethylammonium tetraphenylboranate, cethyltrimethylammonium phenolate, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or guanidine systems such as l,5,7-triazabicyclo[4,4.0]-dec-5-ene (TBD), 7- Phenyl-l,5,7-triazabicyclo-[4,4,0]-dec-5-ene, 7-methyl-l,5,7-triazabicyclo-[4,4,0]-dec-5-ene, 7,7'-hexylidenedi-l,5,7-triazabi-cyclo-[4,4,0]-dec-5-ene, 7,7'-Decylidenedi-l,5,7-triazabicyclo- [4,4,0]-dec-5-ene, 7,7'-dodecylidene-di-1,5,7-tri-aza-bicyclo-[4,4,0]-dec-5-ene or phosphazenes such as the phosphazene base Pl-t-Oct = tert. -Octyl -imino-tris- (dimethylamino)-phosphorane, phosphazene base Pl-t-butyl = tert. -Butyl -imino-tris- (dimethylamino)-phosphorane, BEMP = 2 -tert. -Butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diaza-2-phos-phoran, in question.

[0107] 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 14 -aryls, 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.

[0108] Particularly preferred catalysts are monobutyltin oxide, dibutyltin oxide, lithium hydroxide, lithium acetate dihydrate, and 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 particularly preferred. Sodium methylate is also preferred.

[0109] These catalysts are preferably used in amounts of 1* 10' 6 up to l* 10 -4 Mol, especially preferably 1 * 10' 5 up to 5* 10' 5 Mole based on 1 mol of all diisocyanate component(s) used. The amounts of alcoholates can be used in the range from 0.1 to 100 ppm, preferably 0.5 to 50 ppm, and particularly preferably 1 to 30 ppm, based on the total starting materials (diol(s) + diisocyanate(s) + diaryl carbonate).

[0110] Short description of the characters:

[0111] Figure 1: GPC spectrum of a prepolymer (Example 2b) based on TCDDM and H12-MDI in a molar ratio of 2:1 (diol:diisocyanate) plotted against the molar mass. Figure 2: Illustration of the subdivision of the GPC spectrum of a prepolymer (Example 2b) for determining the arithmetic mean of the repeating unit "m" of the prepolymer and 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 11) based on TCDDM and H12-MDI in a molar ratio of 10:1 (diol:diisocyanate) plotted against the molar mass.

[0112] Figure 4: Illustration of the subdivision of the GPC spectrum of a prepolymer (Example 11) for determining the arithmetic mean of the repeating unit "m" of the prepolymer and the residual diol content; the designations A to E represent individual peaks that must therefore be considered separately.

[0113] Figure 5: 13 C-NMR spectrum of a poly(urethane-co-carbonate) (Example 21) based on CHDM and H12-MDI in the molar ratio of 2:1 (diol: diisocyanate).

[0114] Figure 6: 13 C-NMR spectrum of a poly(urethane-co-carbonate) (Example 46) based on TCD-DM and H12-MDI in the molar ratio of 2:1 (diol: diisocyanate).

[0115] Examples

[0116] Materials used:

[0117] Diol component (according to formula (1a) according to the invention)

[0118] CHDM (1) 1,4-Cyclohexanedimethanol: Mixture of c7.s- l .4-Cyclohcxandimethanol and trara- 1,4-Cyclohexanedimethanol, CAS: 105-08-8, 99%, Sigma Aldrich, Germany, was used without further purification

[0119] / rara-CHDM (1) trara- 1,4-Cyclohexanedimethanol, CAS: 3236-48-4, 97.77%, BLDpharm, China, was used without further purification

[0120] TCD-DM (2) Tricyclodecanedimethanol: mixture of isomers, CAS: 26896-48-0, 96%, Sigma Aldrich, Germany, was used without further purification

[0121] Diol component (comparison)

[0122] ISB Polysorb PS A: Isosorbide, CAS: 652-67-5, 99.8%, Roquette Freres,

[0123] France, was used without further cleaning

[0124] HD 1,6-Hexanediol, CAS: 629-11-8, 97%, Sigma Aldrich, Germany, was used without further purification

[0125] Diisocyanate component (according to the invention according to formula (Ila))

[0126] H12-MDI (3) l,l'-Methylenebis(4-isocyanatocyclohexane): mixture of isomers, CAS: 5124-30-1, Covestro AG, Germany, was used without further purification

[0127] Diisocyanate component (comparison if it is the only diisocyanate component or also according to the invention as an additional diisocyanate component)

[0128] HDI hexamethylene diisocyanate, CAS: 822-06-0, Covestro AG, Germany, was used without further purification

[0129] IPDI Isophorone diisocyanate: Mixture of cA-isophorone diisocyanate and

[0130] / rara-Isophorone diisocyanate. CAS: 4098-71-9, Covestro AG, Germany, was used without further purification. MDI Diphenylmethane-4,4'-diisocyanate, CAS: 101-68-8, Covestro AG,

[0131] Germany, was stored at 45 °C and used without further purification

[0132] TDI Toluene-2,4-diisocyanate, CAS: 584-84-9, Covestro AG, Germany, was used without further purification

[0133] Carbonyl source

[0134] DPC Diphenyl Carbonate, CAS: 102-09-0, Covestro AG, Germany, was freshly distilled before use

[0135] catalyst

[0136] Katl Monobutyltin oxide, CAS: 2273-43-0, TIB Chemicals AG, Germany, was used without further purification

[0137] Cat2 TBD: l,5,7-triazabicyclo(4.4.0)dec-5-ene, CAS: 5807-14-7, 98%, Sigma

[0138] Aldrich, Germany, was used without further purification

[0139] Solvent

[0140] MCB Monochlorobenzene, CAS: 108-90-7, Azelis, Germany, was used without further purification

[0141] Analytical methods:

[0142] GPC:

[0143] 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 with slow shaking. The sample was then filtered through a 0.45 pm PTFE filter and analyzed using a suitable GPC system with an SDV column. Calibration was performed using narrowly distributed polystyrene standards (e.g., ReadyCal Kit Polystyrene low, nominal Mp 266-66,000 Da) and adjusted to the columns and samples. THF was used as the eluent. Detection was performed using ultraviolet radiation (UV) and refractive index (refractive index detector, RI for short). The general method is defined by Currenta GmbH & Co. OHG under AM 2011-0623701-09D, which can be requested from Currenta at any time. Determination of the arithmetic mean of the repeating unit m and residual diol amount in

[0144] Prepolymers using example 2b

[0145] 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)), 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 2b in Figure 1). The determination of this arithmetic mean repeating unit of m and the residual diol amount is explained below using Example 2b.

[0146] Both the m of the prepolymers and the remaining unreacted diol in wt% were determined from the GPC spectra plotted against the elution volume. 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 spectrum of Example 2b in Figure 2).

[0147] The GPC spectrum in Figure 2 for Example 2b yielded the following areas F (in %):

[0148] 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”, see above)

[0149] B: Prepolymer with repeating unit m = 4 (F = 9.9%)

[0150] C: Prepolymer with repeating unit m = 3 (F = 15.3%)

[0151] D: Prepolymer with repeating unit m = 2 (F = 22.4%)

[0152] E: Prepolymer with repeating unit m = 1 (F = 27.7%)

[0153] F: unknown (F = 0.3%)

[0154] G: Residual diol CHDM (F = 12.0%)

[0155] According to the weighted arithmetic mean, m was determined.

[0156] 1 x F(m = 1) + 2 x F(m = 2) + — I- nx F(m = ri) m = -

[0157] F prepolymer)

[0158] With F(prepolymer) = 87.7% 1 x I + 2 x 22.4 + 3 x 15.3 + 4 x 9.9 + > 5 x 12.4

[0159] 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.

[0160] 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 11 (see Figure 3).

[0161] The GPC spectrum in Figure 4 for Example 11 resulted in the following areas F (in %):

[0162] A: Prepolymer with repeating unit m = 3 (F = 0.7%)

[0163] B: Prepolymer with repeating unit m = 2 (F = 4.9%)

[0164] C: Prepolymer with repeating unit m = 1 (F = 24.8%)

[0165] D: unknown (F = 0.9%)

[0166] E: residual diol TCD-DM (F = 68.7%)

[0167] According to the weighted arithmetic mean, m was determined.

[0168] With F(prepolymer) = 30.4%

[0169] 1 x 24.8 + 2 x 4.9 + 3 x 0.7

[0170] DSC:

[0171] The glass transition temperature (Tg) was determined by differential scanning calorimetry (DSC) according to DIN EN ISO 11357-1:2009-10 and ISO 11357-2:2013-05 at a heating rate of 20 K / min under nitrogen as the inflection point in the second heating process.

[0172] 'H-NMR spectroscopy:

[0173] H NMR spectroscopy revealed almost complete incorporation (> 97%) of the diol and diisocyanate components into the polymer. Determination of the aromatic groups in the poly(urethane-co-carbonate):

[0174] The proportion of aromatic hydrocarbons (aromaticity) in poly(urethane-co-carbonate)s, which is implemented through the use of aromatic diisocyanates such as MDI and TDI, was determined using 'H NMR spectroscopy. For this purpose, approximately 20 mg of sample was dissolved in a suitable solvent (chloroform-dl or DMSO-d6) and measured on a Bruker AV III HD 600 NMR spectrometer at a measurement frequency of 600.4 MHz. Measurement parameters:

[0175] Pulse program pulprog zg30

[0176] Scan per increment NS: 64

[0177] Relaxation time between two scans Dl: 3 see

[0178] It was generally assumed that the poly(urethane-co-carbonate)s (Examples 34-37), which are partly based on aromatic diisocyanates, comprise polyurethane components made of aromatic diisocyanates and diol, as well as aliphatic diisocyanates and diol, and polycarbonate components made of diol. From the proportion of the polyurethane made of aromatic diisocyanates and diol, the aromaticity could be determined using the molecular weight of the repeat unit of the polyurethane and the proportion of aromatic hydrocarbons it contains.

[0179] For the poly(urethane-co-carbonate)s based on CHDM, MDI, and H12-MDI (Examples 34 and 35), the integral value (also called area, F for short) of the chemical shift signal of 7.1 ppm was chosen for the assignment of the polyurethane from MDI and CHDM, which can be assigned to 4 CH protons on the MDI. For the assignment of the polyurethane from H12-MDI and CHDM, the integral value of the signal at 4.2-5.0 ppm was chosen, which can be assigned to 2 CH2 protons on the H12-MDI. For the assignment of the polycarbonate from CHDM, the integral value of the CH2 signal at 3.1-4.2 ppm was chosen, which, in addition to the 4 CH2 protons on the carbonate functionality, can also be assigned to the 6 CH2 protons of the polyurethane from MDI and CHDM and the polyurethane from H12-MDI and CHDM.Therefore, for the integral value of the signal at 3.1-4.2 ppm, the proportional integral value of 6 protons of the respective polyurethanes must be subtracted to obtain the integral for the 4 CH2 protons of the polycarbonate from CHDM.

[0180] The proportion in mol% of the aromatic polyurethane from MDI and CHDM is given by the following formula: F (7.1 ppm) 10Q

[0181] Arom. PU content (mol-%)

[0182] " > x . ,F (7.1 ppm) F(4, 2-5.0 ppm).

[0183] F(7.1 ppm) F(4.2-5.0 ppm) , f (3.1-4.2 ppm) - 6 ■ ( - ? - )

[0184] 4 + 2 + 4

[0185] Using the molecular weight of the repeating unit of the polyurethane from MDI and CHDM of 394.5 g / mol and the proportion of aromatics contained therein with a molecular weight of 152.2 g / mol, the proportion of aromatic groups can be calculated from the relative proportion of the aromatic polyurethane from MDI and CHDM for the poly(urethane-co-carbonate)s based on CHDM, MDI and H12-MDI (Examples 34 and 35) using the following formula:

[0186] " ,, 152.2 g / mol

[0187] Aromaticity (mol-%) = - - — - - x Arom. PU content (mol-%)

[0188] 394.5 g / mol

[0189] For the poly(urethane-co-carbonate)s based on CHDM, TDI, and H12-MDI (Examples 36 and 37), the integral value (also called area, abbreviated F) of the chemical shift signal of 2.2 ppm was chosen for the assignment of the polyurethane from MDI and CHDM, which can be assigned to three CH2 protons on the TDI. For the assignment of the polyurethane from H12-MDI and CHDM, the integral value of the signal at 4.3-4.9 ppm was chosen, which can be assigned to two CH2 protons on the H12-MDI. For the assignment of the polycarbonate from CHDM, the integral value of the CH2 signal at 3.2-4.2 ppm was chosen. This signal, in addition to the 4 CH2 protons on the carbonate functionality, can also be assigned to the 4 CFF protons of the polyurethane from TDI and CHDM, as well as to the 6 CH2 protons of the polyurethane from H12-MDI and CHDM. Therefore, for the integral value of the signal at 3.1-4.2 ppm, the proportional integral value of 4 or 5 ppm must be used.6 protons of the respective polyurethanes are subtracted to obtain the integral for the 4 CH2 protons of the polycarbonate from CHDM.

[0190] The proportion in mol% of the aromatic polyurethane from TDI and CHDM is given by the following formula:

[0191] F (2.2 ppm) 10Q

[0192] Arom. PU content (mol-%)

[0193] " . "

[0194] 3 + 2 + 4

[0195] Using the molecular weight of the repeating unit of the polyurethane from TDI and CHDM of 318.4 g / mol and the proportion of aromatics contained therein with a molecular weight of 75.1 g / mol, the proportion of aromatic groups can be calculated from the relative proportion of the aromatic polyurethane from TDI and CHDM for the poly(urethane-co-carbonate)s based on CHDM, TDI and H12-MDI (Examples 36 and 37) according to the following formula:

[0196] Calculate formula:

[0197] " ,, 75.1

[0198] Aromaticity (mol%) = -

[0199] 318.4

[0200] It is clear to the person skilled in the art that when using aromatic diisocyanates other than MDI and TDI and diols other than CHDM, other signals must be used to classify the polyurethane(s) and polycarbonate and thus to determine the aromaticity.

[0201] 13 C NMR spectroscopy:

[0202] The ratio of urethane to carbonate groups in the poly(urethane-co-carbonate)s was determined by 13 C NMR spectroscopy. For this purpose, 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.

[0203] Measurement parameters:

[0204] Pulse program pulprog zgig30

[0205] Scan per increment NS: 512

[0206] Relaxation time between two scans Dl: 4

[0207] The following illustrates the evaluation of the urethane to carbonate group ratio using Example 21 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.

[0208] Assignment for the determination of urethane to carbonate from the 13 C NMR spectrum

[0209] Urethane signal at 156 ppm

[0210] Carbonate signal at 155.5 ppm

[0211] The molar ratio results directly from the areas of the respective signals normalized to 100.

[0212] From the 13 C-NMR spectrum in Figure 5 gives the following estimated molar ratio: Urethane = 65

[0213] Carbonate = 35 Evaluation of the urethane to carbonate group ratio for Example 46 for a poly(urethane-co-carbonate) based on tricyclodecanedimethanol (TCD-DM) and H12-MDI in the molar ratio of 2:1 (diol:diisocyanate)

[0214] Assignment for the determination of urethane to carbonate from the 13 C NMR spectrum

[0215] Urethane signal at 156 ppm

[0216] Carbonate signal at 155.5 ppm

[0217] The molar ratio results directly from the areas of the respective signals normalized to 100.

[0218] From the 13 C-NMR spectrum in Figure 6 gives the following estimated molar ratio: Urethane = 66

[0219] Carbonate = 34

[0220] Hydroxyl number:

[0221] 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 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.

[0222] NCO value:

[0223] The NCO content was determined titrimetrically according to DIN EN ISO 11909:2007-05.

[0224] Production of urethanediols (UDO) as precursors of poly(urethane-co-carbonate)s (PUC)

[0225] Example 1: Reaction of CHDM (according to formula (1)) as diol component with H12-MDI (according to formula (3)) as diisocyanate building block in a molar ratio of 3:2 (diol.diisocyanate) in the presence of cat.

[0226] 123.75 g (858 mmol) of CHDM and 0.015 g (100 ppm based on H12-MDI) of Katl 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 was 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 prepolymer with an OH number of 118.3 mg KOH / g and M was obtained. n of 1630 g / mol.

[0227] Example 2a: Reaction of CHDM (according to formula (1)) as diol component with H12-MDI (according to formula (3)) as diisocyanate building block in a molar ratio of 2:1 (diol.diisocyanate).

[0228] 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 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 prepolymer with an OH number of 207.7 mg KOH / g and M was obtained. n of 830 g / mol.

[0229] Example 2b: Reaction of CHDM (according to formula (1)) as diol component with H12-MDI (according to formula (3)) as diisocyanate building block in a molar ratio of 2:1 (diol.diisocyanate) in the presence of cat.

[0230] 440 g (3.05 mol) of CHDM and 0.04 g (100 ppm based on H12-MDI) of Katl 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 with stirring at atmospheric pressure. 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 prepolymer with an OH number of 204.7 mg KOH / g and M was obtained. n of 780 g / mol.

[0231] Example 3: Reaction of CHDM (according to formula (1)) as diol component with H12-MDI (according to formula (3)) as diisocyanate building block in a molar ratio of 3:1 (diol.diisocyanate).

[0232] 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 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 prepolymer with an OH number of 314.5 mg KOH / g and M was obtained. n of 550 g / mol. Example 4: Reaction of CHDM (according to formula (1)) as the diol component with H12-MDI (according to formula (3)) as the diisocyanate building block in a molar ratio of 4:1 (diol:diisocyanate) in the presence of catalyst.

[0233] 880 g (6.10 mol) of CHDM and 0.040 g (100 ppm based on H12-MDI) of Katl 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 4 h at 100 °C. The temperature was then increased 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 prepolymer with an OH number of 384.5 mg KOH / g and M was obtained. n of 460 g / mol.

[0234] Example 5: Reaction of CHDM (according to formula (1)) as diol component with H12-MDI (according to formula (3)) as diisocyanate building block in a molar ratio of 10:1 (diol.diisocyanate).

[0235] 550 g (4.58 mol) of CHDM 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 130 °C for 60 minutes. After 60 minutes, a sample was taken in a nitrogen countercurrent for NCO measurement. The NCO value was 0%, and the reaction was stopped. A colorless prepolymer with an OH number of 588.9 mg KOH / g and M was obtained. n of 300 g / mol.

[0236] Example 6: Reaction of trans-CHDM (according to formula (1)) as diol component with H12-MDI (according to formula (3)) as diisocyanate building block in a molar ratio of 2:1 (diol.diisocyanate).

[0237] 50.0 g (0.35 mol) of ms-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 at atmospheric pressure with stirring. 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 prepolymer with an OH number of 189.5 mg KOH / g and M n of 930 g / mol.

[0238] (according to formula (3)) as a diisocyanate building block in a molar ratio of 3:2 (diol.diisocyanate).

[0239] 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 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 prepolymer with an OH number of 104.4 mg KOH / g and M was obtained. n of 1200 g / mol.

[0240] (according to formula (3)) as a diisocyanate building block in a molar ratio of 2:1 (diol.diisocyanate).

[0241] 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 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 prepolymer with an OH number of 170.9 mg KOH / g and M was obtained. n of 750 g / mol.

[0242] (according to formula (3)) as a diisocyanate building block in a molar ratio of 3:1 (diol.diisocyanate).

[0243] 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 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 prepolymer with an OH number of 263.0 mg KOH / g and M was obtained. n of 420 g / mol.

[0244] (according to formula (3)) as a diisocyanate building block in a molar ratio of 4:1 (diol.diisocyanate).

[0245] 150 g (0.76 mol) of TCD-DM and 50 g (0.19 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 prepolymer with an OH number of 321.0 mg KOH / g and M was obtained. n of 330 g / mol.

[0246] Example 11: Reaction of TCD-DM (according to formula (2)) as diol component with H12-MDI (according to formula (3)) as diisocyanate building block in a molar ratio of 10:1 (diol.diisocyanate).

[0247] 500 g (2.55 mol) of TCD-DM and 50 g (0.25 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 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 colorless prepolymer with an OH number of 448.8 mg KOH / g and M was obtained. n of 230 g / mol.

[0248] Example 12: Reaction of CHDM (according to formula (1)) as diol component with H12-MDI (according to formula (3)) as diisocyanate building block in a molar ratio of 2:1 (diol.diisocyanate) in the presence of Katl with subsequent distillation of the excess CHDM.

[0249] 440 g (3.05 mol) of CHDM and 0.040 g (100 ppm based on H12-MDI) of Katl were placed in a flask equipped with a reflux condenser and 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 prepolymer with an OH number of 137.7 mg KOH / g and M n of 1130 g / mol.

[0250] Example 13: Reaction of CHDM (according to formula (1)) as the diol component with H12-MDI (according to formula (3)) as the diisocyanate building block in a molar ratio of 3:1 (diol:diisocyanate) in the presence of Katl, followed by distillation of the excess CHDM. 330 g (2.29 mol) of CHDM and 0.020 g (100 ppm based on H12-MDI) of Katl were placed in a flask equipped with a reflux condenser and dropping funnel. The mixture was melted under a nitrogen blanket and heated to 100 °C at atmospheric pressure with stirring. 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 hours, 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. Distillation of the unreacted monomer-diol CHDM was carried out under reduced pressure (<1 mbar) at a bath temperature of 175 °C. After distillation, a yellowish prepolymer with an OH number of 118.3 mg KOH / g and M was obtained. n of 1660 g / mol.

[0251] Example 14: Reaction of CHDM (according to formula (1)) as diol component with H12-MDI (according to formula (3)) as diisocyanate building block in a molar ratio of 4:1 (diol.diisocyanate) in the presence of Katl with subsequent distillation of the excess CHDM.

[0252] 440 g (3.05 mol) of CHDM and 0.02 g (100 ppm based on H12-MDI) of Katl were placed in a flask equipped with a reflux condenser and 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 distillation, a yellowish prepolymer with an OH number of 141.5 mg KOH / g and M was obtained. n of 1330 g / mol.

[0253] Example 15: Reaction of CHDM (according to formula (1)) as the diol component with H12-MDI (according to formula (3)) as the diisocyanate building block in a molar ratio of 10:1 (diol:diisocyanate) in the presence of Katl, followed by distillation of the excess CHDM. 550 g (3.81 mol) of CHDM and 0.01 g (100 ppm based on H12-MDI) of Katl were placed in a flask equipped with a reflux condenser and dropping funnel. The mixture was melted under a nitrogen blanket and heated to 100 °C at atmospheric pressure with stirring. 100 g (0.38 mmol) of H12-MDI was added dropwise via the dropping funnel over a period of 3 h at 100 °C. The temperature was then increased to 130 °C, and the mixture was stirred for 1 h at 130 °C. After 1 h, a sample was taken in a nitrogen counterflow 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. Distillation of the unreacted monomer-diol CHDM was carried out under reduced pressure (<1 mbar) at a bath temperature of 200 °C. After distillation, a yellowish prepolymer with an OH number of 216.7 mg KOH / g and M was obtained. n of 640 g / mol.

[0254] Table 1: Comparison of the results of examples 1 to 15.

[0255] Production of urethanediols (UDO) as precursors of poly(urethane-co-carbonate)s (PUC) using aromatic diisocyanates

[0256] Example 16: Reaction of CHDM (according to formula (1)) as diol component with H12-MDI (according to formula (3), A) and MDI (B) in a weight ratio of 9:1 as diisocyanate building blocks in a molar ratio of 2:1 (diol:diisocyanateA+B).

[0257] 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 at atmospheric pressure with stirring. 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 prepolymer with an OH number of 192.3 mg KOH / g and M was obtained. n of 820 g / mol.

[0258] Example 17: Reaction of CHDM (according to formula (1)) as diol component with Hl 2-MDI (according to formula (3), A) and MDI (B) in a weight ratio of 1:1 as diisocyanate building blocks in a molar ratio of 2:1 (diol:diisocyanateA+B).

[0259] 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 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 prepolymer with an OH number of 210.9 mg KOH / g and M was obtained. n of 790 g / mol.

[0260] Example 18: Reaction of CHDM (according to formula (1)) as diol component with Hl 2-MDI (according to formula (3), A) and TDI (B) in a weight ratio of 9:1 as diisocyanate building blocks in a molar ratio of 2:1 (diol:diisocyanateA+B).

[0261] 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 prepolymer with an OH number of 198.8 mg KOH / g and M was obtained. n of 750 g / mol.

[0262] Example 19: Reaction of CHDM (according to formula (1)) as diol component with Hl 2-MDI (according to formula (3), A) and TDI (B) in a weight ratio of 1:1 as diisocyanate building blocks in a molar ratio of 2:1 (diol:diisocyanateA+B).

[0263] 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 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 prepolymer with an OH number of 206.8 mg KOH / g and M was obtained. n of 740 g / mol. Table 2: Comparison of the results of Examples 16 to 19.

[0264] Production of poly(urethane-co-carbonate)s (PUC) by polycondensation of previously prepared urethanediols (UDO) with diphenyl carbonate (PPC)

[0265] Example 20: Reaction of Example 1 as UDO component with DPC as carbonyl source in a molar ratio of 1:1 (UDO.DPC) in the presence of cat.

[0266] 75.0 g (79.1 mmol) of Example 1 (OH number: 118.3 mgKOH / g) and 16.94 g (79.1 mmol) of DPC, as well as 0.002 g (22 ppm based on the starting materials Example 1 and DPC) of Katl 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, while continuously removing phenol. 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 (approx. 0.4 mbar) and condensation continued for another 60 minutes. After that, the reaction was stopped. A light yellow polymer with a M w of 72,600 g / mol.

[0267] Example 21: Reaction of Example 2a as UDO component with DPC as carbonyl source in a molar ratio of 1:1.03 (UDO.DPC) in the presence of cat.

[0268] 150.0 g (277.6 mmol) of Example 2a (OH number: 207.7 mgKOH / 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 2a and DPC) of Katl 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 (approx. 0.6 mbar), and condensation was continued for a further 60 minutes. The reaction was then stopped. A light yellow polymer with a M w of 86,700 g / mol.

[0269] Example 22: Reaction of Example 2b as UDO component with addition of 0.5 eq. CHDM (according to formula (1)) with DPC as carbonyl source in a molar ratio of 1:1 ((UDO+0.5 eq. CHDM):DPC) in the presence of cat.

[0270] 75.0 g (137.2 mmol) of another batch of Example 2b (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 2b, CHDM, and DPC) of Katl 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, before the pressure was further reduced to < 1 mbar (approx. 0.6 mbar) within 20 minutes and condensed for another 60 minutes. The mixture was then stirred for 4 h at 220 °C under high vacuum (approx. 0.4 mbar). The reaction was then stopped. A light yellow polymer with a M w of 92,700 g / mol.

[0271] Example 23: Reaction of Example 2b as UDO component with addition of 1.0 eq. CHDM (according to formula (1)) with DPC as carbonyl source in a molar ratio of 1:1 ((UDO + 1.0 eq. CH M): PC) in the presence of cat.

[0272] 75.0 g (137.2 mmol) of another batch of Example 2b (OH number: 205.3 mgKOH / g), 19.64 g (136.2 mmol) of CHDM, 58.34 g (272.3 mmol) of DPC, and 0.008 g (52 ppm based on the starting materials of Example 2b, CHDM, and DPC) of Katl were placed in a flask equipped with a Vigreux column and distillation bridge. The mixture was melted under a nitrogen blanket and heated to 160 °C with stirring at atmospheric pressure. The mixture was stirred for 30 minutes at 160 °C and for 20 minutes at 190 °C. Subsequently, a vacuum was applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 30 minutes. The mixture was stirred for 30 minutes at 190 °C before the pressure was further reduced to < 1 mbar (approx. 0.8 mbar) over 10 minutes. Stirring was then continued for 4 h at 220 °C under high vacuum (approx. 0.4 mbar). The reaction mixture was then stopped. A light yellow polymer with a M w of 190,800 g / mol.

[0273] Example 24: Reaction of Example 2b as UDO component with addition of 1.5 eq. CHDM (according to formula (1)) with DPC as carbonyl source in a molar ratio of 1:1 ((UDO + 1.5 eq. CHDM):DPC) in the presence of cat.

[0274] 75.0 g (137.2 mmol) of another batch of Example 2b (OH number: 205.3 mgKOH / g), 29.46 g (204.3 mmol) of CHDM, 72.93 g (340.4 mmol) of DPC, and 0.010 g (56 ppm based on the starting materials of Example 2b, CHDM, and DPC) of Katl 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 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 60 minutes at 190 °C, for 10 minutes at 200 °C, and for 20 minutes at 220 °C. The pressure was then reduced to < 1 mbar (approx. 0.6 mbar), and condensation was continued for another 4 hours. The reaction was then stopped. A light yellow polymer with a M w of 250,300 g / mol.

[0275] Example 25: Reaction of Example 2b as UDO component with addition of 2.0 eq. CHDM (according to formula (1)) with DPC as carbonyl source in a molar ratio of 1:1 ((UDO+2.0 eq. CH M): PC) in the presence of cat.

[0276] 75.0 g (137.2 mmol) of another batch of Example 2b (OH number: 205.3 mgKOH / g), 39.28 g (272.4 mmol) of CHDM, 87.51 g (408.5 mmol) of DPC, and 0.012 g (59 ppm based on the starting materials of Example 2b, CHDM, and DPC) of Katl 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 160 °C and for 20 minutes at 190 °C. Subsequently, a vacuum was applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 50 minutes. The mixture was stirred for 30 minutes at 190 °C before the pressure was further reduced to < 1 mbar (approx. 0.9 mbar) over a period of 20 minutes. Stirring was then continued for 4 hours at 220 °C under high vacuum (approx. 0.7 mbar). The reaction mixture was then stopped. A light yellow polymer with a M wof 122,100 g / mol. Example 26: 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 catalyst.

[0277] 75.0 g (210.2 mmol) of Example 5 (OH number: 314.5 mgKOH / g), 45.03 g (210.2 mmol) of DPC, and 0.006 g (50 ppm based on the starting materials Example 3 and DPC) of Katl 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 with stirring at atmospheric pressure. 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 (approx. 0.4 mbar) and condensation continued for another 4 h. The reaction was then stopped. A light yellow polymer with a M w of 52,700 g / mol.

[0278] Example 27: Reaction of Example 4 as UDO component with DPC as carbonyl source in a molar ratio of 1:1 (UDO.DPC) in the presence of cat.

[0279] 75.0 g (257.0 mmol) of Example 4 (OH number: 384.5 mgKOH / g), 55.05 g (257.0 mmol) of DPC, and 0.007 g (54 ppm based on the starting materials Example 4 and DPC) of Katl 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 with stirring at atmospheric pressure. The mixture was stirred for 20 minutes at 150 °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 500 mbar over 10 minutes. The mixture was stirred for 30 minutes at 190 °C before the pressure was reduced to 100 mbar over 10 minutes. After a 30-minute holding phase, the bath temperature was increased to 220 °C, the pressure was reduced to < 1 mbar (approx. 0.3 mbar), and the mixture was condensed for a further 4 h. The reaction was then stopped. A light yellow polymer with a M w of 78,200 g / mol.

[0280] Example 28: Reaction of Example 5 as UDO component with DPC as carbonyl source in a molar ratio of 1:1 (UDO.DPC) in the presence of cat.

[0281] 75.0 g (393.6 mmol) of Example 5 (OH number: 588.9 mgKOH / g), 82.0 g (382.8 mmol) of DPC, and 0.011 g (70 ppm based on the starting materials Example 5 and DPC) of Katl 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 with stirring at atmospheric pressure. The mixture was stirred for 20 minutes at 150 °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 800 mbar over 10 minutes. The mixture was stirred for 30 minutes at 190 °C before the pressure was reduced to 100 mbar over 10 minutes. After a 30-minute holding phase, the bath temperature was increased to 220 °C, the pressure was reduced to < 1 mbar (approx. 0.3 mbar), and the mixture was condensed for a further 4 h. The reaction was then stopped. A light yellow polymer with a M w of 52,000 g / mol.

[0282] Example 29: 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.

[0283] 75.0 g (126.7 mmol) of Example 6 (OH number: 189.5 mgKOH / g), 27.13 g (126.6 mmol) of DPC, and 0.004 g (39 ppm based on the starting materials Example 6 and DPC) of Katl 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 polymer with a M w of 50,300 g / mol.

[0284] Example 30: Reaction of Example 12 as UDO component with DPC as carbonyl source in a molar ratio of 1:1 (UDO.DPC) in the presence of cat.

[0285] 150.0 g (184.1 mmol) of Example 12 (OH number: 137.7 mgKOH / g), 39.43 g (184.1 mmol) of DPC, and 0.007 g (37 ppm based on the starting materials Example 12 and DPC) of Katl were placed in a flask equipped 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 (approx. 0.4 mbar) and the mixture was condensed for a further 2 h. The reaction was then stopped. A light yellow polymer with a M w of 68,300 g / mol.

[0286] Example 31: Reaction of Example 13 as UDO component with DPC as carbonyl source in a molar ratio of 1:1 (UDO.DPC) in the presence of Katl.

[0287] 75.0 g (79.1 mmol) of Example 13 (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 Example 13 and DPC) of Katl 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 (approx. 0.3 mbar) within 10 minutes, and the mixture was condensed for a further 60 minutes. After that, the reaction was stopped. A light yellow polymer with a M w of 93,300 g / mol.

[0288] Example 32: Reaction of Example 14 as UDO component with DPC as carbonyl source in a molar ratio of 1:1 (UDO.DPC) in the presence of cat.

[0289] 75.0 g (94.6 mmol) of Example 14 (OH number: 141.5 mgKOH / g), 20.26 g (94.6 mmol) of DPC, and 0.003 g (31 ppm based on the starting materials Example 14 and DPC) of Katl 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 at atmospheric pressure with stirring. The mixture was stirred for 15 minutes at 150 °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 5 minutes and the bath temperature was increased to 220 °C over 15 minutes. The mixture was stirred at 220 °C for 80 minutes. The pressure was then reduced to < 1 mbar (approx. 0.4 mbar) within 15 minutes, and the mixture was condensed for a further 60 minutes. After that, the reaction was stopped. A light yellow polymer with a M w of 80,500 g / mol.

[0290] Example 33: Reaction of Example 15 as the UDO component with DPC as the carbonyl source in a molar ratio of 1:1 (UDO:DPC) in the presence of Catl. 150.0 g (289.7 mmol) of Example 15 (OH number: 216.7 mgKOH / g), 62.05 g (289.7 mmol) of DPC, and 0.007 g (33 ppm based on the starting materials Example 15 and DPC) of Catl 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 10 minutes at 150 °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 < 1 mbar (approx. 0.3 mbar) within 30 minutes. The mixture was heated to 210 °C within 30 minutes and condensed for a further 4 h. The reaction was then stopped. A light yellow polymer with a M w of 30,300 g / mol.

[0291] Example 34: Reaction of Example 16 as UDO component with DPC as carbonyl source in a molar ratio of 1:1.11 (UDO: DPC) in the presence of cat.

[0292] 150.0 g (257.1 mmol) of Example 16 (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 16 and DPC) of Katl 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 with stirring at atmospheric pressure. 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 (approx. 0.5 mbar), and the mixture was condensed for a further 60 minutes. The reaction was then stopped, yielding a yellow polymer with an M w of 73,800 g / mol.

[0293] Example 35: Reaction of Example 17 as UDO component with DPC as carbonyl source in a molar ratio of 1:1.03 (UDO.DPC) in the presence of cat.

[0294] 75.0 g (141 mmol) of Example 17 (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 17 and DPC) of Katl 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 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 gradually heated to 240 °C over 105 minutes. The pressure was then reduced to < 1 mbar (approx. 0.2 mbar) and the mixture was condensed for a further 90 minutes. After this time, the reaction was stopped. A yellow polymer with a M w of 127,900 g / mol.

[0295] Example 36: Reaction of Example 18 as UDO component with DPC as carbonyl source in a molar ratio of 1:1.10 (UDO.DPC) in the presence of cat.

[0296] 75.0 g (132.9 mmol) of Example 18 (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 18 and DPC) of Katl 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 with stirring at atmospheric pressure. The mixture was stirred for 20 minutes at 130 °C and for 30 minutes at 180 °C. A vacuum was then applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 30 minutes. The mixture was then gradually heated to 240 °C over 60 minutes. The pressure was then reduced to < 1 mbar (approx. 0.9 mbar), and the mixture was condensed for a further 60 minutes. The reaction was then stopped, yielding a yellow polymer with an M w of 79,600 g / mol.

[0297] Example 37: Reaction of Example 19 as UDO component with DPC as carbonyl source in a molar ratio of 1:1.14 (UDO.DPC) in the presence of cat.

[0298] 75.0 g (138.2 mmol) of Example 19 (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 Example 19 and DPC) of Katl 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 with stirring at atmospheric pressure. 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 < 1 mbar (approx. 0.5 mbar), and the mixture was condensed for a further 60 minutes. The reaction was then stopped, yielding a yellow polymer with an M w of 43,300 g / mol. Table 3: Comparison of the results of Examples 20 to 37.

[0299] * E stands for invention and V for comparative example

[0300] * * By bending the solidified melt by hand, a first impression was gained. The material is called "ductile" if it did not break. Otherwise, it is called "brittle."

[0301] Production of poly(urethane-co-carbonate)s (PUC) - One-Pot

[0302] Example 38: Reaction of CHDM (according to formula (1)) as diol component with H12-MDI (according to formula (3)) as diisocyanate building block and DPC as carbonyl source in a molar ratio of 2:1:1.05 (diol.diisocyanate.DPC) in the presence of cat.

[0303] 110 g (0.76 mol) of CHDM, 100 g (0.38 mol) of H12-MDI, 86.0 g (0.40 mol) of DPC, and 0.01 g (34 ppm based on the starting materials CHDM, H12-MDI, and DPC) of Katl were placed in a flask equipped with a Vigreux column and distillation bridge. 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. It was then heated to 180 °C and stirred at 180 °C for 30 minutes. A vacuum was then applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 10 minutes, and the bath temperature was increased to 240 °C over 2 h. The mixture was stirred at 240 °C for 20 minutes. The pressure was then reduced to < 1 mbar (approx. 0.2 mbar) within 60 minutes, and the mixture was condensed for a further 1 h. The reaction was then stopped. A light yellow polymer with a M w of 61,000 g / mol.

[0304] Production of poly(urethane-co-carbonate)s (PUC) - Sequential One-Pot

[0305] Example 39: Reaction of CHDM (according to formula (1)) as diol component with H12-MDI (according to formula (3)) as diisocyanate building block in the presence of Katl and subsequent reaction with DPC as carhonyl source in a molar ratio of 2:1:1.05 (diol.diisocyanate.DPC).

[0306] 220 g (1.53 mol) of CHDM, 200 g (0.76 mol) of H12-MDI, and 0.02 g (48 ppm based on the CHDM and H12-MDI feedstocks) of Katl were placed in a flask equipped with a Vigreux column and distillation bridge. 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%. After a further 30 minutes, 163.7 g (0.76 mol) of DPC were added in a nitrogen countercurrent. The mixture was heated to 180 °C and stirred at 180 °C for 20 minutes. Vacuum was then applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar within 10 minutes and the bath temperature was increased to 220 °C within 80 minutes. The mixture was stirred for 10 minutes at 220 °C. The pressure was then reduced to < 1 mbar (approx. 100 °C) within 35 minutes.0.2 mbar) and the mixture was condensed for a further 4 h. The reaction was then stopped. A light yellow polymer with a M. w of 68,800 g / mol.

[0307] Example 40: Reaction of CHDM (according to formula (1)) as the diol component with H12-MDI (according to formula (3)) as the diisocyanate building block and subsequent reaction with DPC as the carhonyl source in a molar ratio of 2:1:1 (diol.diisocyanate.DPC) in the presence of catalyst. 220 g (1.53 mol) of CHDM and 200 g (0.76 mol) of H12-MDI were placed in a flask fitted with a Vigreux column and distillation bridge. The mixture was melted under a blanket of nitrogen and heated to 130°C at atmospheric pressure with stirring. The mixture was stirred for 2 h at 130°C. After 2 h, 163.7 g (0.76 mol) of DPC and 0.02 g (34 ppm based on the starting materials CHDM, H12-MDI and DPC) of catalyst were added in a countercurrent of nitrogen. The mixture was heated to 180 °C and stirred at 180 °C for 20 minutes. Vacuum was then applied to continuously remove phenol. The pressure was reduced to 100 mbar over 10 minutes and the bath temperature was increased to 220 °C over 10 minutes.The mixture was stirred for 45 minutes at 220 °C. The pressure was then reduced to < 1 mbar (approx. 0.4 mbar) within 35 minutes, and the mixture was condensed for a further 2 hours. The reaction was then stopped. A light yellow polymer with a M was obtained. w of 114,700 g / mol.

[0308] Example 41: Reaction of ISB as diol component (comparison) with H12-MDI (according to formula (3)) as diisocyanate building block in the presence of Kat1 and subsequent reaction with DPC as carhonyl source in a molar ratio of 2:1:1 (diol.diisocyanate.DPC) with addition of Kat2.

[0309] 167.3 g (1.14 mol) of ISB and 0.017 g (113 ppm based on H12-MDI) of Katl were placed in a flask equipped with a reflux condenser and dropping funnel. The mixture was melted under a nitrogen blanket and heated to 100 °C with stirring at atmospheric pressure. 150 g (0.57 mol) of H12-MDI were added dropwise via the dropping funnel over a period of 2 h. The temperature was then increased to 150 °C, and the mixture was stirred for 4 h at 150 °C. After 4 h, a sample was taken for NCO measurement in a nitrogen countercurrent. The NCO value was 0%. The reaction mixture was shut off and remained in the flask overnight. The polycondensation 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 head was installed. The mixture was melted under nitrogen blanket and heated to 180 °C at atmospheric pressure while stirring.After 45 minutes, 121.4 g (0.57 mol) of DPC and 0.017 g (113 ppm based on H12-MDI) of Kat2 were added in a nitrogen counterflow. The mixture was heated to 200 °C and stirred for 30 minutes. Vacuum was then applied to continuously remove phenol. For this purpose, the pressure was reduced to < 1 mbar (approx. 0.4 mbar) within 100 minutes, and the bath temperature was gradually increased to 240 °C. The mixture condensed for a further 4 h at 240 °C. The reaction was then stopped. A dark brown polymer with a M was obtained. w of 16,600 g / mol. Example 42: Reaction of HD as the diol component (comparison) with H12-MDI (according to formula (3)) as the diisocyanate building block in the presence of Katl and subsequent reaction with DPC as the carhonyl source in a molar ratio of 2:1:1 (diol.diisocyanate.DPC) with renewed addition of Katl.

[0310] 47.47 g (402 mmol) of HD, 0.003 g (57 ppm based on H12-MDI) of Katl, and 100 g of MCB were placed in a flask equipped with a reflux condenser and dropping funnel. The mixture was heated to 120 °C with stirring under a nitrogen blanket at atmospheric pressure. 52.63 g (201 mmol) of H12-MDI was added dropwise via the dropping funnel over a period of 20 minutes. The mixture was then stirred at 120 °C for 2 h. After 2 h, a sample was taken for NCO measurement in a nitrogen countercurrent. The NCO value was 0%. The reaction mixture was shut off and remained in the flask overnight. The polycondensation 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 head was installed. 43.16 g (201 mmol) of DPC and 0.005 g (105 ppm based on HD) of Katl were added to the mixture. The reaction mixture was heated to 170 °C under nitrogen at ambient pressure and stirred for 20 minutes.Subsequently, a vacuum was applied to continuously remove MCB and phenol. The pressure was reduced to < 1 mbar (approximately 0.5 mbar) over 80 minutes, and the bath temperature was gradually increased to 220 °C. The mixture was condensed for a further 4 h at 220 °C. The reaction was then stopped. A light yellow polymer with a M was obtained. w of 80,900 g / mol.

[0311] Example 43: Reaction of CHDM (according to formula (1)) as diol component with IPDI as diisocyanate building block (comparison) in the presence of Katl and subsequent reaction with DPC as carbonyl source in a molar ratio of 2:1:1 (diol.diisocyanate.DPC) with renewed addition of Katl.

[0312] 168 g (1.16 mol) of CHDM, 0.017 g (131 ppm based on IPDI) of Katl, and 162 g of MCB were placed in a flask equipped with a reflux condenser and dropping funnel. The mixture was heated to 120 °C with stirring under a nitrogen blanket at atmospheric pressure. 129.5 g (0.58 mol) of IPDI was added dropwise via the dropping funnel over a period of 75 minutes. The mixture was then stirred at 120 °C for 4 hours. After 4 hours, a sample was taken for NCO measurement in a nitrogen countercurrent. The NCO value was 0%. The reaction mixture was shut off and remained in the flask for two nights. The polycondensation was carried out the day after next. For this purpose, the dropping funnel and reflux condenser were removed, and a Vigreux column with a connected distillation head was installed. 124.8 g (0.58 mol) of DPC and 0.017 g (131 ppm based on IPDI) of Katl were added to the mixture. The reaction mixture was heated to 170 °C to 190 °C under a nitrogen blanket at atmospheric pressure with stirring.Most of the MCB was distilled off under atmospheric pressure for 40 minutes. A vacuum was then applied to remove the remaining MCB and continuously remove phenol. To this end, the pressure was reduced to < 1 mbar (approx. 0.6 mbar) over 90 minutes, and the bath temperature was gradually increased to 220 °C. The mixture was condensed for a further 4 h at 220 °C. The reaction was then stopped. A yellow polymer with a M was obtained. w of 129,800 g / mol.

[0313] Example 44: Reaction of CHDM (according to formula (1)) as diol component with HDI as diisocyanate building block (comparison) in the presence of Katl and subsequent reaction with DPC as carhonyl source in a molar ratio of 2:1:1 (diol.diisocyanate.DPC) with renewed addition of Katl.

[0314] 63.23 g (438 mmol) of CHDM, 0.006 g (163 ppm based on HDI) of Katl, and 100 g of MCB were placed in a flask equipped with a reflux condenser and dropping funnel. The mixture was heated to 120 °C under a nitrogen blanket at atmospheric pressure with stirring. 36.76 g (219 mmol) of HDI was added dropwise via the dropping funnel over a period of 75 minutes. The mixture was then stirred at 120 °C for 6 hours. The reaction mixture was then shut off and left in the flask for six nights. Six days later, the polycondensation was carried out. For this purpose, the dropping funnel and reflux condenser were removed, and a Vigreux column with a connected distillation head was installed. 47.03 g (220 mmol) of DPC and 0.005 g (136 ppm based on HDI) of Katl were added to the mixture. The mixture was heated to 170 °C to 200 °C under nitrogen at atmospheric pressure with stirring. MCB was largely distilled off under atmospheric pressure for 70 minutes.Subsequently, a vacuum was applied to remove the remaining MCB and continuously remove phenol. To this end, the pressure was reduced to < 1 mbar (approx. 0.4 mbar) within 50 minutes and the bath temperature was gradually increased to 220 °C. The mixture condensed for a further 15 minutes at 220 °C. The reaction was then stopped. A yellow polymer was obtained, the M. w could not be determined due to low solubility.

[0315] Example 45: Reaction of TCD-DM (according to formula (2)) as the diol component with H12-MDI (according to formula (3)) as the diisocyanate building block and subsequent reaction with DPC as the carbonyl source in a molar ratio of 3:2:1.05 (diol.diisocyanate.DPC) in the presence of catalyst. 56.12 g (286 mmol) of TCD-DM and 50 g (191 mmol) of H12-MDI 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, and stirred for 2 h at 130 °C. After 2 h, 21.43 g (100 mmol) of DPC and 0.003 g (24 ppm based on the starting materials TCD-DM, H12-MDI and DPC) of catalyst were added in a nitrogen countercurrent. The mixture was heated to 180 °C and stirred for 20 minutes. Vacuum was then applied to continuously remove phenol. The pressure was reduced to 100 mbar over 10 minutes.The mixture was stirred for 40 minutes at 180 °C, for 20 minutes at 190 °C, for 20 minutes at 220 °C, and for 20 minutes at 240 °C. The pressure was then reduced to < 1 mbar (approx. 0.3 mbar) within 30 minutes, and the mixture was condensed for a further 1 h. The reaction was then stopped. A light yellow polymer with a M was obtained. w of 51,000 g / mol.

[0316] Example 46: Reaction of TCD-DM (according to formula (2)) as diol component with H12-MDI (according to formula (3)) as diisocyanate building block and subsequent reaction with DPC as carhonyl source in a molar ratio of 2:1:1 (diol.diisocyanate.DPC) in the presence of catalyst.

[0317] 74.86 g (381 mmol) of TCD-DM and 50 g (191 mmol) of H12-MDI were placed in a flask fitted with a Vigreux column and a distillation bridge. The mixture was melted under a nitrogen blanket and heated to 130 °C under stirring at atmospheric pressure, where it was stirred for 2 h. After 2 h, 40.93 g (191 mmol) of DPC and 0.005 g (30 ppm based on the starting materials TCD-DM, H12-MDI, and DPC) of Katl were added in a nitrogen countercurrent. The mixture was heated to 180 °C and stirred for 40 minutes. 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 30 minutes at 190 °C, for 10 minutes at 200 °C, for 10 minutes at 210 °C, and for 10 minutes at 220 °C. The pressure was then reduced to < 1 mbar (approx. 0.3 mbar) within 15 minutes, and the mixture was condensed for a further 4 hours. The reaction was then stopped.A light yellow polymer with an M was obtained. w of 76,000 g / mol.

[0318] Example 47: Reaction of TCD-DM (according to formula (2)) as the diol component with H12-MDI (according to formula (3)) as the diisocyanate building block and subsequent reaction with DPC as the carhonyl source in a molar ratio of 3:1:2 (diol.diisocyanate.DPC) in the presence of catalyst. 56.12 g (286 mmol) of TCD-DM and 25 g (95.3 mmol) of H12-MDI were placed in a flask equipped 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, and stirred for 2 h at 130 °C. After 2 h, 40.83 g (191 mmol) of DPC and 0.005 g (41 ppm based on the starting materials TCD-DM, H12-MDI, and DPC) of catalyst were added in a nitrogen countercurrent. The mixture was heated to 180 °C and stirred for 20 minutes. Vacuum was then applied to continuously remove phenol. 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 10 minutes at 200 °C, for 10 minutes at 210 °C, and for 10 minutes at 220 °C. The pressure was then reduced to < 1 mbar (approx. 0.3 mbar) over 15 minutes, and the mixture was condensed for a further 4 hours. The reaction was then stopped. A light yellow polymer with a M. w of 75,600 g / mol.

[0319] Example 48: Reaction of TCD-DM (according to formula (2)) as diol component with H12-MDI (according to formula (3)) as diisocyanate building block and subsequent reaction with DPC as carhonyl source in a molar ratio of 4:1:3 (diol.diisocyanate.DPC) in the presence of catalyst.

[0320] 59.83 g (305 mmol) of TCD-DM and 20 g (76.2 mmol) of H12-MDI were placed in a flask fitted with a Vigreux column and a distillation bridge. The mixture was melted under a nitrogen blanket and heated to 130 °C under stirring at atmospheric pressure, then stirred for 2 h at 130 °C. After 2 h, 48.99 g (229 mmol) of DPC and 0.006 g (47 ppm based on the starting materials TCD-DM, H12-MDI, and DPC) of Katl were added in a nitrogen countercurrent. The mixture was heated to 180 °C and stirred for 20 minutes. 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 and for 10 minutes at 220 °C. The pressure was then reduced to < 1 mbar (approx. 0.6 mbar) within 15 minutes, and the mixture was condensed for a further 4 h. The reaction was then stopped. A light yellow polymer with a M w of 31,900 g / mol.

[0321] Example 49: Reaction of TCD-DM (according to formula (2)) as the diol component with H12-MDI (according to formula (3)) as the diisocyanate building block and subsequent reaction with DPC as the carhonyl source in a molar ratio of 10:1:9 (diol.diisocyanate.DPC) in the presence of catalyst. 74.82 g (381 mmol) of TCD-DM and 10 g (38.1 mmol) of H12-MDI 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, and stirred for 2 h at 130 °C. After 2 h, 73.49 g (343 mmol) of DPC and 0.009 g (57 ppm based on the starting materials TCD-DM, H12-MDI and DPC) of catalyst were added in a nitrogen countercurrent. The mixture was heated to 180 °C and stirred for 20 minutes. Vacuum was then applied to continuously remove phenol. The pressure was reduced to 100 mbar over 5 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 (approx. 0.6 mbar) within 10 minutes, and the mixture was condensed for a further 3 hours. The reaction was then stopped. A light yellow polymer with a M was obtained. w of 34,500 g / mol.

[0322] Table 4: Comparison of the results of examples 38 to 49.

[0323] * E stands for invention and V for comparative example

[0324] * * By bending the solidified melt by hand, a first impression was gained. The material is called "ductile" if it did not break. Otherwise, it is called "brittle."

Claims

Patent claims:

1. Thermoplastic poly(urethane-co-carbonate) comprising structures of formulas (I) and (II), wherein where each R 1 in formula (I) each independently represents an aliphatic group having 6 to 18 carbon atoms, which has at least one cycle and which 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 wherein 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 less than 58 mol% to greater than 0 mol%, preferably less than 58 mol% to greater than 15 mol% carbonate groups based on the sum of the carbonate and urethane groups in the poly(urethane-co-carbonate), wherein the mol percent of carbonate and urethane groups is above, 13 C-NMR spectroscopy and that the thermoplastic poly(urethane-co-carbonate) has a weight average molecular weight of 40,000 g / mol to 200,000 g / mol.

2. Thermoplastic poly(urethane-co-carbonate) according to claim 1, characterized in that it has no ether groups and / or no ester groups.

3. Thermoplastic poly(urethane-co-carbonate) according to claim 1 or 2, characterized in that the thermoplastic poly(urethane-co-carbonate) has at most 60 mol% of aromatic groups, this amount being based on the total amount of aliphatic and aromatic groups.

4. Thermoplastic poly(urethane-co-carbonate) according to claim 1 to 3, comprising the structural formula (III) where each R 1 has the meanings given for formula (I), where the group -CFE-R'-CFE- enclosed by the round brackets also partly independently of one another represents R 6 provided that at least part of the structures is -CFE-R'-CFE-, and R 6 represents an aliphatic alkylene group having 4 to 20 carbon atoms, which may be linear, branched or 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 7means 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 and m is the arithmetic mean of the repeating units and is a number between 1.7 and 5.0 and the wavy lines represent the connection of the structure of formula (III) into the chain of the poly(urethane-co-carbonate).

5. Thermoplastic poly(urethane-co-carbonate) according to one of claims 1 to 4, characterized in that the thermoplastic poly(urethane-co-carbonate) has a glass transition temperature above 90 °C.

6. Thermoplastic poly(urethane-co-carbonate) according to one of claims 1 to 5, characterized in that R 1 in formula (I) or in formula (III) 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 CFF groups shown in formula (I) and formula (III) are located, respectively.

7. Thermoplastic poly(urethane-co-carbonate) according to one of claims 1 to 6, characterized in that the structure R 2 in formula (II) or formula (III) 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 (II) and formula (III) 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.

8. A molding composition containing the thermoplastic poly(urethane-co-carbonate) according to any one of claims 1 to 7.

9. A molded article containing the thermoplastic poly(urethane-co-carbonate) according to any one of claims 1 to 7.

10. A process for producing the thermoplastic poly(urethane-co-carbonate) according to any one of claims 1 to 7, comprising the process steps (i) Reaction of at least one aliphatic diol of formula (Ia) HO — CH2— R1 - CH2— OH , , . . , ni • a), where each R in d JI? 1 n (l of formula (Ia A) each independently represents an aliphatic group having 6 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) . . 1 1 1 (11a), where R in formula (11a) represents a bridging aliphatic structure having 6 to 18 carbon atoms, where said bridging structure has at least one cycle and said cycle may optionally contain at least one heteroatom and where the bridging structure is attached to the nitrogen atoms shown in structure (IIa) 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 3.7: 1 to 1.3:

1.

11. The process according to claim 10, 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.

12. The process according to claim 10 or 11, characterized in that the at least one catalyst present in process step (ii) is an ammonium salt, a phosphonium salt or an organic base.

13. Method according to one of claims 10 to 12, characterized in that R 1 in formula (la) is represented by formula (1) or formula (2), where the positions marked with the star in formulas (1) and (2) are the Positions at which the CTU groups shown in formula (la) are located.

14. The method according to any one of claims 10 to 13, characterized in that the structure R 2 in formula (Ila) 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) 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.

15. The method according to claim 14, characterized in that R 2in formula (Ila) is represented by the structure of formula (3), where p = 0 and q = 1. .

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