thermoplastic poly(urethane-co-carbonate)

Abstract

The present invention relates to thermoplastic poly(urethane-co-carbonate)s and a process for their preparation. The poly(urethane-co-carbonate)s have a weight average molar mass of at least 40 000 g / mol and have a specific ratio of carbonate groups to urethane groups.

Description

[0001] This invention relates to thermoplastic poly(urethane-co-carbonate) and its preparation method.

[0002] Aromatic polycarbonates are renowned for their excellent mechanical, optical, heat distortion, and weather resistance properties. However, the presence of aromatic groups necessitates improvements in transmittance, birefringence, and yellowing tendency. In contrast, aliphatic polycarbonates offer improved properties in the same range, as well as in chemical resistance; however, they typically have low glass transition temperatures and consequently lower heat distortion resistance. Therefore, efforts are being made to provide aliphatic polycarbonates with overall improved performance.

[0003] In EP 2 883 898 A1, aliphatic polycarbonate is blended with polyurethane. The mechanical properties of the aliphatic polycarbonate can be improved by forming an IPN (interpenetrating polymer network). This aliphatic polycarbonate is polypropylene carbonate or polyethylene carbonate. Therefore, it contains a linear aliphatic structure, which typically has a low glass transition temperature (approximately 25-45°C). Furthermore, the examples in this document only use aromatic diisocyanates. These typically increase the glass transition temperature of the blend, but due to their aromatic groups, they also introduce the aforementioned disadvantages (especially yellowing tendency, poor transmittance, and birefringence).

[0004] WO 2013 / 016331 A2 describes polyurethane compositions 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 their molecular weight, these polyols can be liquid or crystalline at room temperature. The polyols containing carbonate groups react with aromatic diisocyanates. The aforementioned disadvantages also arise here due to the introduction of aromatic groups into the polymer structure.

[0005] EP 1 700 877 A1 describes a poly(urethane carbonate) polyol obtained using an aliphatic linear diol and an aliphatic diisocyanate. Here, the molar ratio of diol to diisocyanate is always at least 4:1. Subsequently, the resulting OH-terminated prepolymer is reacted with diphenyl carbonate along with an unreacted excess diol to obtain a poly(urethane carbonate) polyol with a relatively low molar mass (obtainable from the OH value) of about 1000 to 2000 g / mol. The resulting polyol has a glass transition temperature below 0°C. It is first reacted with an aromatic diisocyanate to generate a prepolymer, which is then processed into a cast elastomer by adding a linear diol. Because this document thus relates to the provision of cast elastomers, it does not focus on the glass transition temperature of the polyol, nor does it adjust it to the range required for cast elastomers. These deviate significantly from the preferred ranges for thermoplastic polycarbonate compositions.

[0006] Based on the prior art, the object of the present invention is therefore to overcome at least one disadvantage of the prior art, preferably all disadvantages. In particular, the object of the present invention is to provide a thermoplastic polycarbonate having a glass transition temperature of at least 90°C by (co-)using an aliphatic starting material. By (co-)using an aliphatic starting material, the thermoplastic polycarbonate should have good optical properties (especially transparency). The thermoplastic polycarbonate should preferably also have high heat deformability (although using an aliphatic forming component). The thermoplastic polycarbonate should preferably be processed using plasticizing methods commonly used for aromatic polycarbonates (e.g., injection molding, (co)extrusion, blow molding, deep drawing). For this purpose, it is particularly advantageous that the thermoplastic polycarbonate is amorphous. The thermoplastic polycarbonate should also preferably have good mechanical properties, for example, properties comparable to those of aromatic polycarbonates. The thermoplastic polycarbonate should particularly preferably have at least room-temperature brittle fracture.

[0007] The present invention achieves at least one of the above objectives, preferably all of the above objectives.

[0008] Surprisingly, it has been found that a poly(urethane-co-carbonate) with a minimum molar mass containing at least one particular structure of formula (I) and at least one particular structure of formula (II) and having a specific molar ratio of carbonate groups to the total number of carbonate and urethane groups has a glass transition temperature of at least 90°C. Here, the structure of formula (I) can be obtained, for example, by using an aliphatic primary glycol containing at least one ring. The structure of formula (II) can also be obtained by using a secondary or tertiary diisocyanate containing at least one ring. It has been found that the glass transition temperature can be selectively adjusted by the ratio of carbonate groups to urethane groups in the copolymer, particularly achieving a glass transition temperature of at least 90°C. The ratio of carbonate groups to urethane groups can be adjusted, for example, by the ratio of one diol / multiple diols used to one diisocyanate / multiple diisocyanates used. Furthermore, it can be influenced by selectively adding or removing diols before the prepolymer reacts with the carbonyl source. Similarly, different copolymers with different ratios of carbonate groups to urethane groups can be mixed in blends to specifically adjust the ratios. The thermoplastic poly(urethane-co-carbonate) of the present invention exhibits correspondingly good heat deformation resistance. The glass transition temperature within this range allows the thermoplastic poly(urethane-co-carbonate) of the present invention to be used in conventional plasticizing methods (e.g., injection molding, (co)extrusion, blow molding, deep drawing), and in particular, to possess the "thermoplastic" properties known to those skilled in the art. According to the present invention, the term "thermoplastic" is preferably understood to mean a polymer that can be deformed within a certain temperature range, particularly above room temperature, more preferably above 50°C, and very particularly preferably above 90°C. This deformation is preferably reversible. In particular, the term "thermoplastic" according to the present invention is preferably used to distinguish between thermosetting polymers and / or elastomeric polymers. These thermosetting polymers and / or elastomeric polymers have physical crosslinking of their individual polymer chains, which results in irreversible deformation (beyond the elastic range). Such polymers cannot be deformed / shaped by conventional plasticizing methods.

[0009] The thermoplastic poly(urethane-co-carbonate) of the present invention is amorphous. This, in particular, gives them excellent optical properties. Specifically, the poly(urethane-co-carbonate) of the present invention is transparent. Preferably, the term "transparent" in the present invention should be understood as the transmittance of the injection-molded plate in the spectral VIS range (380 to 780 nm) being at least 20%, preferably at least 50%, more preferably at least 70%, and still preferably at least 80% (transmittance TVIS), as measured according to DIN ISO 13468-2:2006 (D65, 10°, sample plate thickness: 4 mm). Also preferably, the haze of these injection-molded plates is simultaneously less than 30%, preferably less than 20%, very particularly preferably less than 10%, and also particularly preferably less than 7%, as measured according to ASTM D1003:2013. This specifically refers to injection-molded plates with visual transparency, i.e., the ability to display the background.

[0010] Similarly, the thermoplastic poly(urethane-co-carbonate) of the present invention, being amorphous, is particularly suitable for use in known plasticizing methods of aromatic polycarbonates. The advantage of the poly(urethane-co-carbonate) of the present invention is that its properties are similar to those of common aromatic polycarbonates. Because the poly(urethane-co-carbonate) of the present invention is amorphous, it is particularly free from shrinkage. The term "shrinkage" is known to those skilled in the art in the field of polymers, particularly crystalline polymers. Preferably, this term refers to the effect of volume reduction caused by crystal formation during the cooling of the polymer melt. Therefore, the volume and dimensions of the injection-molded part are reduced 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 methods, shrinkage must always be considered for the resulting molded part. Therefore, aromatic polycarbonates cannot be simply replaced by crystalline polymers in standard plasticizing methods.

[0011] Furthermore, the thermoplastic poly(urethane-co-carbonate) of the present invention exhibits good mechanical properties, such as ductile fracture at least at room temperature. Therefore, the thermoplastic poly(urethane-co-carbonate) of the present invention particularly possesses excellent performance characteristics, comparable to, and preferably superior to, conventional aromatic polycarbonates (e.g., bisphenol A-based). Specifically, in addition to good mechanical properties, the thermoplastic poly(urethane-co-carbonate) of the present invention also exhibits good chemical resistance (especially hydrolysis resistance), good transmissivity, good birefringence, and a low tendency to yellow. In a preferred embodiment, the proportion of aromatic groups in the thermoplastic poly(urethane-co-carbonate) of the present invention is limited, particularly very low, thereby reducing, and especially avoiding, the common drawbacks of the presence of aromatic groups in polymers.

[0012] According to the present invention, a thermoplastic poly(urethane-co-carbonate) comprising the structures of formulas (I) and (II) is provided, wherein (I) Where each R in equation (I) 1 Each of the components is an aliphatic group having 6 to 18 carbon atoms, comprising at least one ring, and the ring may optionally contain at least one heteroatom. and (II) Where each R in equation (II) 2 Each is independently a bridged aliphatic structure having 6 to 18 carbon atoms, wherein the bridged structure comprises at least one ring, and the ring may optionally comprise at least one heteroatom, and wherein the connection between the bridged structure and the nitrogen atom shown in structure (II) is made by secondary or tertiary carbon atoms respectively. In formulas (I) and (II), the wavy lines respectively represent the connection of structures of formulas (I) and (II) in the poly(urethane-co-carbonate) chain, and at least some of the structures of formulas (I) and (II) are directly connected to each other to form urethane groups, and at least some other structures (I) are directly connected to each other with at least one other structure of formula (I) to form carbonate groups. Characterized by comprising, in part, less than 58 mol% to greater than 0 mol%, preferably greater than 15 mol% of carbonate groups, based on the sum of carbonate and urethane groups in the poly(urethane-co-carbonate), wherein the molar percentage of carbonate and urethane groups is determined by... 13 The determination was performed by C-NMR spectroscopy, and the weight-average molar mass of the thermoplastic poly(urethane-co-carbonate) was at least 40,000 g / mol.

[0013] According to the present invention, the term "poly(urethane-co-carbonate)" is used to describe polymers having the characteristics of the present invention. This polymer has both urethane and carbonate groups. It is not excluded that the poly(urethane-co-carbonate) of the present invention may also have other functional groups (especially including functional groups with structures different from those of formulas (I) and (II)). However, the poly(urethane-co-carbonate) of the present invention preferably does not contain ether groups and / or ester groups. Therefore, the poly(urethane-co-carbonate) of the present invention preferably does not contain ether groups. The poly(urethane-co-carbonate) of the present invention is particularly preferably free of linear ether groups. This preferably means that the poly(urethane-co-carbonate) of the present invention does not contain polyethylene oxide and / or polypropylene oxide segments. Likewise, it is also preferred, and particularly preferred, that the poly(urethane-co-carbonate) of the present invention does not contain ester groups. According to the present invention, such groups are preferably absent because, according to the present invention, polyether polyols and / or polyester polyols are preferably not used in the production process of the poly(urethane-co-carbonate) of the present invention. Obviously, the components used may contain common impurities, for example, from their production process. Therefore, the poly(urethane-co-carbonate) of the present invention may also contain trace amounts of ether and / or ester groups. However, it is preferable to use components that are as pure as possible. Furthermore, it is apparent that these impurities may be present even in closed formulations.

[0014] It is also preferable to avoid structures that do not contain the structure resulting from direct connection of the structure of formula (II) to the structure of formula (II). This would generate a urea group.

[0015] It will be apparent to those skilled in the art that other functional groups can be incorporated into the poly(urethane-co-carbonate) of the present invention using specific monofunctional chain terminators.

[0016] The poly(urethane-co-carbonate) of the present invention particularly preferably comprises mainly urethane groups and carbonate groups for linking formulas (I) and (II) to each other. The resulting structure constitutes the main part of the polymer chain of the poly(urethane-co-carbonate). For example, by directly linking at least some structures (I) to at least one other structure of formula (I), a structure of formula (IA) can be formed: .

[0017] R 1 The definition is the same as that of formula (I), including all preferred embodiments. Those skilled in the art will understand that carbonate groups are formed by directly linking at least some structures (I) with at least one other structure of formula (I).

[0018] Similarly, by directly connecting at least some of the structures of equations (I) and (II) to each other, the structure of equation (IIA) is formed: (IIA) R 1 and R 2 The definition is the same as that in formulas (I) and (II), including all preferred embodiments. Those skilled in the art will understand that urethane groups are formed by the direct interconnection of at least some of the structures of formulas (I) and (II).

[0019] In the poly(urethane-co-carbonate) of the present invention, the structures of formulas (IA) and (IIA) are preferably randomly distributed. This is especially applicable when other structures different from those of formulas (I) and (II) / (IA) and (IIA) also exist.

[0020] The poly(urethane-co-carbonate) of the present invention is preferably prepared by the method of the present invention, which is described in more detail below. In this method, a diol is first reacted with a diisocyanate. The resulting prepolymer is then reacted with a carbonate source. Through this process sequence, urethane and carbonate groups are primarily generated. Those skilled in the art will understand that other functional groups can also be incorporated into the poly(urethane-co-carbonate) by using specific diols and / or diisocyanates. Furthermore, the urethane and carbonate groups are those groups that constitute the major part of the polymer chain of the poly(urethane-co-carbonate). Particularly preferably, this means that at least 80%, more preferably at least 90%, of the poly(urethane-co-carbonate) consists of the functional groups “urethane” and “carbonate”, wherein the molar percentage is preferably based on all functional groups containing heteroatoms.

[0021] According to the present invention, the poly(urethane-co-carbonate) comprises the structures of formulas (I) and (II). This does not preclude the presence of other structures in the poly(urethane-co-carbonate) of the present invention, particularly between urethane groups and / or carbonate groups. For example, these structures can be introduced by using other diols and / or other diisocyanates. However, preferably, the poly(urethane-co-carbonate) of the present invention is primarily composed of the structures of formulas (I) and (II). Here, those skilled in the art will understand how structures (I) and (II) are proportioned, especially structures (IA) and (IIA) are included. Particularly preferably, the poly(urethane-co-carbonate) of the present invention comprises at least 50% by weight, preferably at least 75% by weight, more preferably at least 80% by weight, very particularly preferably at least 90% by weight, and especially preferably at least 95% by weight of the structures of formulas (I) and (II). Furthermore, those skilled in the art will also understand how structures (I) and (II) are proportioned, especially structures (IA) and (IIA) are included.

[0022] According to the present invention, poly(urethane-co-carbonate) includes the structure of formula (I). (I), Where each R in equation (I) 1 Each is an aliphatic group having 6 to 18 carbon atoms, comprising at least one ring, and the ring may optionally comprise at least one heteroatom, preferably an oxygen atom, wherein the wavy lines in formula (I) each represent the connection of the structure of formula (I) in the poly(urethane-co-carbonate) chain. Clearly, when R 1 When more than one ring is involved, one or more of the 6 to 18 carbon atoms can also be part of two rings.

[0023] Preferably, R 1 Indicates C6 to C 18 Cycloalkylene. "Cycloalkylene" preferably refers to a bridged cycloalkane structure in which two hydrogen atoms are removed from different carbon atoms. It is not excluded that the CH2- group shown in formula (I) is connected via a straight-chain alkylene chain (provided the specified total number of carbon atoms is present and R...). 1 The overall structure comprises at least one ring. The two carbon atoms from which two hydrogen atoms are removed can be arbitrary, i.e., any part of the ring or a straight-chain alkylene ring (if present). Furthermore, the alkylene ring according to the invention can also be connected or fused to at least one other cyclic aliphatic ring via a bridging structure.

[0024] Throughout this invention, unless otherwise stated, the term "alkylene" or "alkylene group" preferably refers to a bridging alkane structure in which two hydrogen atoms are removed from different carbon atoms. In this context, the two hydrogen atoms removed from the two carbon atoms can be removed from any carbon atom in the alkane structure. This means that the two carbon atoms can be adjacent, but not necessarily adjacent. The alkylene can be straight-chain or branched. It is saturated. If the alkylene has only one carbon atom, it is a methylene (-CH2-) that is attached to the other parts of the molecule by two single bonds. Preferably, the alkylene group comprises methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, tert-butylene, n-pentylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, neopentylene, 1-ethylpropylene, n-hexylene, 1,1-dimethylpropylene, 1,2-dimethylpropylene, 1,2-dimethylpropylene, 1-methylpentylene, 2-methylpentylene, 3-methylpentylene, 4-methyl Examples of such structures include pentylene, 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, and 1-ethyl-2-methylpropylene. The choice of these structures may be limited if the definition of the number of carbon atoms differs in this invention.

[0025] R in equations (I), (IA), (IIA) (or equation (III) shown later) 1 Preferably expressed by equation (1) or equation (2), (1) (2) In formulas (1) and (2), the positions marked with an asterisk "*" are the positions of the CH2- groups shown in formulas (I), (IA), (IIA) or (III).

[0026] Very particularly preferably, formula (I) is represented by the following formula (I1) or (I2): (I1) (I2), The wavy lines in formulas (I1) and (I2) respectively represent the connection of the structures of formulas (I1) and (I2) in the poly(urethane-co-carbonate) chain.

[0027] In addition to the structure of formula (I), the poly(urethane-co-carbonate) of the present invention may also include at least one other structure of formula (Ii): (Ii) Where each R in equation (Ii) 6 It is an aliphatic alkylene group having 4 to 20 carbon atoms, preferably 5 to 18 carbon atoms, more preferably 6 to 16 carbon atoms, the alkylene group may be straight-chain or branched or may contain at least one ring, wherein the at least one ring may contain at least one heteroatom, and wherein when R 6 When it contains at least one ring, R 6 At least on one side, preferably on both sides, the structure is not incorporated into structure (Ii) via CH2- groups, and the wavy lines in formula (Ii) each represent the connection of the structure of formula (Ii) in the chain of the poly(urethane-co-carbonate). These structures of formula (Ii) may at least sometimes be directly attached to other structures of formula (Ii) to form carbonate groups, or at least sometimes be attached to the structure of formula (I). Similarly, the structures of formula (Ii) may at least sometimes be attached to the structures of formula (II) to form urethane groups, or at least sometimes be attached to the structures of formula (IIi) as defined later. The structures of formula (Ii) are preferably randomly distributed in the poly(urethane-co-carbonate) of the present invention. Very particularly preferably, the poly(urethane-co-carbonate) of the present invention does not contain the structures of formula (Ii).

[0028] It will be obvious to those skilled in the art that the structure of equation (Ii) does not correspond to that of equation (I).

[0029] Particularly preferably, the poly(urethane-co-carbonate) of the present invention, in addition to the structure of formula (I), also includes at least one other structure of formulas (Iia) to (Iid). (Iia), (Iib), (Iic) (Iid) The wavy lines in formulas (Iia) and (Iid) respectively represent the connection of the structures of these formulas in the poly(urethane-co-carbonate) chain.

[0030] In the poly(urethane-co-carbonate) of the present invention, it is preferred to select other structures of formula (Ii) or preferred structures (Iia) to (Iid) in amounts such that the glass transition temperature of the resulting poly(urethane-co-carbonate) is maintained above 90°C. Furthermore, ductile fracture at room temperature should be present at least. Particularly preferably, the poly(urethane-co-carbonate) of the present invention comprises at most 75 mol%, more preferably at most 60 mol%, also preferably at most 40 mol%, particularly preferably at most 25 mol%, also preferably at most 10 mol%, and very particularly preferably at most 5 mol% of other structures of formula (Ii) or preferred structures (Iia) to (Iid), based on the sum of structures (Ii) (or (Iia) to (Iid)) and structure (I). It will be apparent to those skilled in the art that the term "at most" can include 0 mol%, as this relates to optional other structures of formula (Ii). However, if at least one structure of formula (Ii) or preferred structures of formulas (Iia) to (Iid) must exist, then the term "at most" here means that more than 0 moles are present.

[0031] The poly(urethane-co-carbonate) of the present invention preferably does not contain the structure of formula (Ii), wherein R 6 It represents the -CH2CH2CH2CH2- group.

[0032] According to the present invention, poly(urethane-co-carbonate) includes other structures of formula (II). (II), Where each R in equation (II) 2Each is independently a bridging aliphatic structure having 6 to 18 carbon atoms, wherein the bridging structure comprises at least one ring, and the ring optionally comprises at least one heteroatom, and wherein the connection between the bridging structure and the nitrogen atom shown in structure (II) is respectively via secondary or tertiary carbon atoms, and wherein the wavy lines in formula (II) respectively represent the connection of the structure of formula (II) in a poly(urethane-co-carbonate) chain. Clearly, the at least one or two secondary or tertiary carbon atoms, each connected to the nitrogen atom shown in the structure of formula (II), may be part of the at least one ring, or part of a different ring. Similarly, the terms "secondary" and "tertiary carbon atom" are known to those skilled in the art. Preferably, this means that the secondary carbon atom is connected to two other carbon atoms (and the two other substituents may be freely chosen, but are not carbon atoms), and the tertiary carbon atom is connected to three other carbon atoms (and the other substituents may be freely chosen, but are not carbon atoms). If applied to formula (II) of the present invention, this means that the secondary carbon atom is connected to two other carbon atoms and one nitrogen atom, wherein the last substituent may be freely chosen (but is not a carbon atom). Similarly, in the case of formula (II) of the present invention, this means that the tertiary carbon atom is attached to three other carbon atoms and one nitrogen atom.

[0033] Preferably, R 2 It is based on the above preferred definition of C6 to C 18 cycloalkylene compounds, wherein, taking into account, as with respect to R 2 The limitations are shown.

[0034] Particularly preferred is the structure R in formulas (II), (IIA) (or formula (III) shown later). 2 It can be expressed by one of equations (3) to (8): (3) (4) (5) (6) (7) (8) In equations (3) to (8), the positions marked with an asterisk "*" indicate the positions of the nitrogen atoms shown in equations (II), (IIA), or (III); and In equation (3), each R 3 Each is independently methyl or ethyl, p is 0, 1, or 2, q is 0 or 1, and In equation (5), each R 3 They are methyl or ethyl, and p is 0, 1 or 2.

[0035] Very particularly preferred, R 2The structure is represented by equation (3), where p = 0 and q = 1. More preferably, the structure of equation (3) (where p = 0 and q = 1) can be a mixture of different structures. Preferred are mixtures of 4,4-linked and 2,4-linked structures, and optionally 2,2-linked structures. Furthermore, preferred are mixtures in which at least 80 mol% of the structure has 4,4-linked connections and the remainder has 2,4- or 2,2-linked connections.

[0036] In addition to the structure of formula (II), the poly(urethane-co-carbonate) of the present invention may also contain at least one other structure of formula (IIi): (IIi) Where each R in equation (IIi) 7 yes - Straight-chain alkylene compounds containing 4 to 12 carbon atoms, - Containing 5 to 20, preferably 7 to 18, cyclic aliphatic groups, wherein the structure R 7 The connection of at least one nitrogen atom shown in structure (IIi) is made via a primary carbon atom, or - Aromatic groups having 6 to 18 carbon atoms, and In formula (IIi), the wavy lines each represent the connection of the structure of formula (IIi) in the chain of the poly(urethane-co-carbonate). The structure of formula (IIi) may be at least sometimes attached to the structure of formula (I) to form urethane groups, or at least sometimes attached to the structure of formula (Ii). Preferably, the structures of formula (IIi) are randomly distributed in the poly(urethane-co-carbonate) of the present invention. Very particularly preferably, the poly(urethane-co-carbonate) of the present invention does not contain the structure of formula (IIi).

[0037] Very particularly preferred, the poly(urethane-co-carbonate) of the present invention, in addition to comprising the structure of formula (II), also comprises at least one other structure of formulas (IIia) to (IIih): (IIia), (IIib), (IIic) (IIid) (IIie) (IIif) (IIig) (IIih), in Each R in equation (IIib) 18Each is independently either hydrogen or methyl, and f in formula (IIib) is a number from 1 to 6. Each R in equation (IIid) 3 They are independently methyl or ethyl, with p being 0, 1, or 2. Each R in equation (IIie) 3 Each is independently either methyl or ethyl, p is 0, 1, or 2, and d is independently either 0 or 1. Where each R in equation (IIig) 3 Each is independently methyl or ethyl, p is 0, 1, or 2, q is 0 or 1, and In formulas (IIia) to (IIih), the positions marked with an asterisk "*" represent the positions of the nitrogen atoms shown in formulas (II), (IIA), or (III).

[0038] In the poly(urethane-co-carbonate) of the present invention, the amount of other structures of formula (IIi) or preferred structures (IIia) to (IIih) is preferably selected to maintain the glass transition temperature of the resulting poly(urethane-co-carbonate) above 90°C. Furthermore, ductile fracture is present at least at room temperature. Additionally, the amount of other structures of formula (IIi) may optionally be adjusted to maintain the preferred aromatic ratio of the resulting poly(urethane-co-carbonate), as preferably defined according to the present invention. Particularly preferably, the poly(urethane-co-carbonate) of the present invention comprises up to 95 mol%, particularly preferably up to 93 mol%, also preferably up to 90 mol%, also particularly preferably up to 80 mol%, also preferably up to 70%, also preferably up to 60%, also preferably up to 50%, also preferably up to 40%, also preferably up to 30%, also preferably up to 20%, also preferably up to 10 mol%, and very particularly preferably up to 5 mol% of other structures of formula (IIi) or preferred structures (IIia) to (IIih), based on the sum of structures (IIi) (or (IIia) to (IIih)) and structure (II). Those skilled in the art will understand that the term "most" can include 0 mol%, as this relates to optional other structures of formula (IIi). However, if at least one structure of formula (IIi) or preferred structures of formulas (IIia) to (IIih) must be present, then the term "most" herein means the presence of more than 0 mol%.

[0039] Particularly preferably, the poly(urethane-co-carbonate) of the present invention comprises the structure of formula (I1) and / or formula (I2), and the structure of formula (II), wherein R 2The structure is represented by equation (3), where p = 0 and q = 1. Particularly preferably, the structure of equation (3) (where p = 0 and q = 1) can be a mixture of different structures. Preferred are mixtures of 4,4-linked and 2,4-linked structures, and optionally 2,2-linked structures. Furthermore, preferred are mixtures where at least 80 mol% of the structure has 4,4-linked connections and the remainder has 2,4-linked or 2,2-linked connections.

[0040] According to the present invention, the poly(urethane-co-carbonate) comprises less than 58% to greater than 0%, preferably less than 58% to greater than 15% carbonate groups, based on the sum of carbonate groups and urethane groups in the poly(urethane-co-carbonate), wherein the molar percentage of carbonate groups and urethane groups is determined by... 13 C-NMR spectroscopy was used for determination. Surprisingly, it was found that a polymer with a glass transition temperature of at least 90°C could be prepared using this specific proportion of carbonate groups. Furthermore, the polymer thus exhibits ductile fracture at least at room temperature. Preferably, the poly(urethane-co-carbonate) contains less than 57 mol% to more than 5 mol%, more preferably less than 56 mol% to more than 10 mol%, more preferably less than 53 mol% to more than 17 mol%, also preferably less than 50 mol% to more than 18 mol%, and most preferably less than 48 mol% to more than 20 mol% of carbonate groups, based on the sum of carbonate and urethane groups in the poly(urethane-co-carbonate).

[0041] Carbonate groups and carbamate groups can be passed through 13 C-NMR spectroscopy determination. Those skilled in the art can use this method to determine the proportions of carbonate and urethane groups. For example, the polymer can be dissolved in CDCl3. If an insoluble residue appears, dimethyl sulfoxide-d6 can also be used as a solvent. More preferably, tetramethylsilane is used as a standard. It has been found that a 600 MHz NMR spectrometer is generally sufficient to distinguish the individual carbon signals of urethane and carbonate groups. The chemical shift of the carbon signal for urethane groups is typically around 156 ppm. The chemical shift of the carbon atom for carbonate groups is typically at 155.5 ppm (see Experimental Section). To determine the molar percentage ratio of carbon atoms, the areas under the signal are integrated and set to ratios. This is a method known to those skilled in the art.

[0042] Furthermore, the weight-average molar mass of the poly(urethane-co-carbonate) of the present invention is at least 40,000 g / mol. Preferably, the weight-average molar mass of the poly(urethane-co-carbonate) of the present invention is from 40,000 g / mol to 200,000 g / mol, more preferably from 50,000 g / mol to 150,000 g / mol, even more preferably from 52,000 g / mol to 100,000 g / mol, and most preferably from 55,000 g / mol to 90,000 g / mol. It has been found that within this specific molar mass range, the poly(urethane-co-carbonate) of the present invention exhibits good properties, particularly good thermoplasticity. Similarly, within this molar mass range, its mechanical properties, particularly its toughness behavior at least at room temperature, are good. It has also been found that if aromatic groups are present in the poly(urethane-co-carbonate) of the present invention, a lower molar mass can optionally be present, but good mechanical properties, particularly ductility, can still be achieved. This preference means that when the poly(urethane-co-carbonate) of the present invention does not contain aromatic groups, its weight-average molar mass 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 most preferably from 55,000 g / mol to 90,000 g / mol. It also preferably means that when the poly(urethane-co-carbonate) of the present invention contains aromatic groups, its weight-average molar mass is from 40,000 g / mol to 200,000 g / mol, particularly preferably from 41,000 g / mol to 150,000 g / mol, especially preferably from 42,000 g / mol to 100,000 g / mol, and most preferably from 43,000 g / mol to 90,000 g / mol.

[0043] Preferably, unless otherwise specified, the weight-average molar mass (M) of the present invention is... w All and / or other molecular weights are determined in tetrahydrofuran using polystyrene as a standard by gel permeation chromatography (preferably based on DIN 55672-1:2007-08, using polystyrene calibration). Calibration is performed using a narrow-distribution polystyrene standard (e.g., ReadyCal Kit low molecular weight polystyrene, nominal molecular weight 266-66000 Da). This general method is defined by Currenta GmbH & Co. OHG in AM 2011-0623701-09D, which is readily available from Currenta. Tetrahydrofuran (THF) is 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, selected to achieve adequate separation of polymer molar masses, particularly the weight-average molar mass M according to the invention.w The polymer concentration ranges from 2000 to 100000 g / mol. Detection can be performed by ultraviolet radiation (UV) and / or refractive index.

[0044] Preferably, the thermoplastic poly(urethane-co-carbonate) of the present invention has at most 60 mol%, preferably at most 58 mol%, more preferably at most 55 mol%, also preferably at most 50 mol%, also preferably at most 45 mol%, also preferably at most 40 mol%, also preferably at most 35 mol%, also preferably at most 30 mol%, also preferably at most 25 mol%, also preferably at most 20 mol%, also preferably at most 15 mol%, also preferably at most 10 mol%, and most preferably at most 5 mol% of aromatic groups, wherein this quantity is based on the total amount of aliphatic and aromatic groups. Obviously, the expression "at most" covers the range from 0 mol% to the indicated mol%. The thermoplastic poly(urethane-co-carbonate) of the present invention is particularly preferably aliphatic. However, as stated above, this does not exclude the presence of trace amounts of aromatic compounds in the polymer due to impurities and / or end groups.

[0045] It has proven advantageous to limit the amount of aromatic groups in the poly(urethane-co-carbonate) of the present invention to minimize the disadvantages caused by the presence of aromatic groups (see above). Aromatic groups may be present in the polymers of the present invention, particularly by the presence of additional structures of formula (Ii) and / or (IIi). The proportion of aromatic groups can be determined by methods known to those skilled in the art. 1 H-NMR spectroscopy is particularly suitable for this purpose.

[0046] The thermoplastic poly(urethane-co-carbonate) of the present invention preferably comprises structural formula (III). (III), Each R 1 The definition is shown in equation (I), where -CH2-R within parentheses 1 -CH2- groups can sometimes be R groups independently of each other. 6 However, this is contingent on at least some structures being -CH2-R. 1 -CH2- and R 6 The definition is shown in equation (Ii), where when R 6 When at least one ring is included, at least on one side, preferably on both sides, the ring is not incorporated into structure (III) via a CH2- group. And each R 2 The definition is shown in equation (II), and R is expressed as follows. 2 / R 7 Represents group R 2 At least sometimes they can be R independently of each other. 7However, this is on the premise that at least some groups are R. 2 And R 7 The definition is shown in equation (IIi). m is the arithmetic mean of the repeating units, a number ranging from 1.7 to 5.0, and the wavy line represents the connection of the structure of formula (III) in the poly(urethane-co-carbonate) chain.

[0047] Those skilled in the art can determine the arithmetic mean m of the number of repeating units using known methods. In particular, m can be determined by gel permeation chromatography; preferably, the gel permeation chromatography described above is used. In this method, different peaks are obtained, which can be assigned to the corresponding oligomers according to their molecular weight. When peaks are not clearly distinguishable (especially in the case of longer-chain oligomers), it is preferable to set the peak breakpoint at the valley between two peaks. If no valley is measured, it is preferable to calculate the peak tailing to the repeating unit corresponding to the maximum value (see also the experimental section and...). Figure 2 and Figure 4 The weighted arithmetic mean m of the repeating units can be calculated based on the area.

[0048] Particularly preferably, in formula (III), the structure -CH2-R 1 -CH2- and R 6 The majority of the sum is structure -CH2-R 1 -CH2-. This means the group -CH2-R 1 -CH2- and R 6 Most of them are incorporated into the polymer chain through secondary carbon atoms.

[0049] Also preferred, and especially preferred, is that in formula (III) group R 2 and R 7 The larger proportion of the total is group R 2 This means that a large proportion of groups are attached to the polymer chain via two secondary and / or tertiary carbon atoms.

[0050] It will be apparent to those skilled in the art how the structure of formula (III) is derived from the structures of formulas (I), (II), (Ii), and / or (IIi). Particularly preferably, formula (III) is represented by the following formula (IIIi). (IIIi), Each R 1 R 2 The definitions of and m are shown in equation (III). Those skilled in the art should understand that equation (IIIi) may also be randomly interrupted due to the existence of equations (Ii) and / or (IIi).

[0051] Furthermore, preferably, the thermoplastic poly(urethane-co-carbonate) of the present invention, in addition to the structure of formula (III) or (IIIi), also includes repeating units of formula (IV). (IV), Each R 1 The definition is shown in equation (I), where -CH2-R within parentheses 1 -CH2- groups can sometimes be R groups independently of each other. 6 And R 6 The definition is shown in formula (Ii), where n is the arithmetic mean of the repeating units, and the wavy line represents the connection of the structure of formula (IV) in the poly(urethane-co-carbonate) chain. If the poly(urethane-co-carbonate) contains 2 to 35% by weight, preferably 3 to 30% by weight, of the groups of formula (IV), the arithmetic mean n is preferably a statistically derived number. Those skilled in the art can determine the proportion of the groups of formula (IV) using their commonly used methods, such as NMR spectroscopy. This method may also depend on the properties of the monomers used.

[0052] Very particularly preferred, the thermoplastic poly(urethane-co-carbonate) inclusion formula (V) structure of the present invention (V) Each R 1 The definition is shown in equation (I), where -CH2-R within parentheses 1 -CH2- groups can sometimes be R groups independently of each other. 6 However, this is contingent on at least some structures being -CH2-R. 1 -CH2- and R 6 The definition is shown in equation (Ii). And each R 2 The definition is shown in equation (II), and R is expressed as follows. 2 / R 7 Represents group R 2 At least sometimes they can be independent of each other for R 7 However, this is on the premise that at least some groups are R. 2 And R 7 The definition is shown in equation (IIi). m and r are each the arithmetic mean of their respective repeating units, where m is a number between 1.7 and 5.0, and x and 1-x are the relative ratios of their respective repeating units to each other.

[0053] Preferably, r is at least 1. Those skilled in the art can correlate r with molecular weight. Clearly, when r is 1, formula (V) is a repeating unit of the poly(urethane-co-carbonate) of the present invention. This repeating unit can be randomly distributed in the poly(urethane-co-carbonate) of the present invention. This repeating unit can also be attached to other repeating units of formula (V). This results in r being greater than 1.

[0054] Those skilled in the art will understand that x must be less than 1.

[0055] It will be apparent to those skilled in the art that the terminal group in formula (V) does not necessarily have to be methyl, but merely represents a potential end of the chain of formula (V), or may be other connection points with other groups.

[0056] Preferably, the glass transition temperature of the thermoplastic poly(urethane-co-carbonate) is higher than 90°C, more preferably higher than 91°C, and even more preferably higher than 95°C. The glass transition temperature (Tg) is preferably determined by dynamic differential scanning calorimetry (DSC) according to DIN EN ISO 11357-1:2009-10 and ISO 11357-2:2013-05 standards. Specifically, a heating rate of 20 K / min is used under a nitrogen atmosphere, and Tg is... g The inflection point in the second heating process was determined. The glass transition temperature within the specified range allows the thermoplastic poly(urethane-co-carbonate) of the present invention to be used in common plasticizing methods (e.g., injection molding, (co)extrusion, blow molding, deep drawing).

[0057] The thermoplastic poly(urethane-co-carbonate) of the present invention can be processed into all types of molded articles. It can also be processed with other thermoplastics and / or polymer additives to form thermoplastic molding compounds, which are then molded into articles. Other subjects of the invention are molded articles and molding compounds containing the thermoplastic poly(urethane-co-carbonate) of the present invention. The polymer additives are preferably selected from flame retardants, anti-drip agents, flame retardant synergists, smoke suppressants, lubricants and release agents, nucleating agents, antistatic agents, conductive additives, stabilizers (e.g., hydrolysis stabilizers, heat aging stabilizers, and transesterification inhibitors), flow promoters, phase compatibilizers, dyes and pigments, impact modifiers, and fillers and reinforcing agents.

[0058] Molded articles containing the thermoplastic poly(urethane-co-carbonate) of the present invention can be produced, for example, by injection molding, extrusion and blow molding. Another processing method is to produce molded parts by deep drawing pre-produced sheets or films.

[0059] Another aspect of the present invention provides a method for producing thermoplastic poly(urethane-co-carbonate), comprising the following method steps: (i) Making at least one aliphatic diol of formula (Ia) Where each R in equation (Ia) 1 Each of the components is an aliphatic group having 6 to 18 carbon atoms, comprising at least one ring, and the ring may optionally contain at least one heteroatom. Reaction with at least one aliphatic diisocyanate of formula (IIa) Where R in equation (IIa) 2 It is a bridged aliphatic structure having 6 to 18 carbon atoms, wherein the bridged structure comprises at least one ring and the ring may optionally comprise at least one heteroatom, and wherein the connection between the bridged structure and the nitrogen atom shown in structure (IIa) is made by secondary or tertiary carbon atoms respectively. To form prepolymers, and (ii) Reacting the prepolymer obtained in step (i) with diaryl carbonate in the presence of at least one catalyst to obtain poly(urethane-co-carbonate). The method is characterized in that, in step (i), the molar ratio of all the diols used to all the diisocyanates used is 3.7:1 to 1.3:1, preferably 3.6:1 to 1.4:1, also preferably 3.5:1 to 1.5:1, and particularly preferably 2.5:1 to 1.8:1.

[0060] Those skilled in the art will recognize the connection between the method of the present invention and the thermoplastic poly(urethane-co-carbonate) of the present invention. In particular, the connection between formulas (Ia) and (IIa) and formulas (I), (II), (III), (IV) and (V) will be apparent.

[0061] The method of the present invention is preferably characterized by producing the thermoplastic poly(urethane-co-carbonate) of the present invention by means of all embodiments, preferred embodiments, and combinations of preferred embodiments. Another aspect of the present invention provides a thermoplastic poly(urethane-co-carbonate) obtained by the method of the present invention. This is preferably the thermoplastic poly(urethane-co-carbonate) of the present invention.

[0062] The final ratio of carbonate groups to urethane groups in poly(urethane-co-carbonate) can be particularly affected by the molar ratio of all the diols used, especially the aliphatic diols of formula (Ia), to all the diisocyanates used, especially the aliphatic diisocyanates of formula (IIa).

[0063] In method step (i), at least one aliphatic diol of formula (Ia) is used. Clearly, only aliphatic diols of formula (Ia) can be used as the sole diol. R in formula (Ia) 1 Preferably, R has the characteristics described in formula (I) above. 1 The definition of . It is especially obvious if R 1 If more than one ring is involved, one or more of the 6 to 18 carbon atoms can also be part of two rings. R in formula (Ia) 1 The preferred option is C6-C as described above. 18 Cycloalkylene oxide. Most preferably, the method of the present invention is characterized in that R in formula (Ia) 1 Expressed by equation (1) or equation (2), (1) (2) In formulas (1) and (2), the positions marked with an asterisk "*" are the positions of the CH2 groups shown in formula (Ia).

[0064] In addition to the aliphatic diol of formula (Ia), one or more other diols may be used in method step (i). Preferably, the amount of the one or more other diols used in method step (i) is at most 75 mol%, more preferably at most 60 mol%, even more preferably at most 40 mol%, even more preferably at most 25 mol%, even more preferably at most 10 mol%, and most preferably at most 5 mol%, based on the total amount of all diols used.

[0065] One or more other diols in method step (i) are preferably at least one diol of formula (X). HO-R 6 -OH (X), Each R 6 The meaning is as shown in formula (Ii). However, preferably, diols containing ether groups are not used in step (i) of the method of the present invention. Also preferably, diols containing ester groups are not used in step (i) of the method of the present invention. In particular, polyether polyols and / or polyester polyols are not used in step (i) of the method of the present invention. Those skilled in the art can also deduce particularly preferred diols from the above preferred embodiments with respect to formula (Ii).

[0066] In this context, it should be understood that the invention frequently refers to "at least one" compound, such as a diol or diisocyanate, and "other" compounds. The compound described as "at least" is essential, while the other compounds (one or more) may be present additionally. Therefore, those skilled in the art can also determine the ratio of diol to diisocyanate.

[0067] In method step (i), at least one aliphatic diisocyanate of formula (IIa) is also used. Clearly, only aliphatic diisocyanates of formula (IIa) can be used as the sole diisocyanate. Here, R in formula (IIa) 2 Preferably, R has the characteristics described in formula (II) above. 2 The definition of . In particular, considering the definition of R. 2 The restrictions imposed, R 2 Representing C6 to C according to the above preferred definition 18 Cycloalkylene compounds. The method of the present invention is particularly preferred in that: Structure R in equation (IIa) 2 Represented by one of equations (3) to (8), (3) (4) (5) (6) (7) (8) In equations (3) to (8), the positions marked with an asterisk "*" are the positions of the nitrogen atoms shown in equation (IIa); In equation (3), each R 3 Each is independently methyl or ethyl, p is 0, 1, or 2, q is 0 or 1, and In equation (5), each R 3 They are methyl or ethyl, and p is 0, 1 or 2.

[0068] Particularly preferably, in method step (i) of the method of the present invention, an aliphatic diol of formula (Ia) is used, wherein R 1 Having the structure of formula (1) and / or (2), and formula (IIa), where R 2 The structure is represented by equation (3), where p = 0 and q = 1. Preferably, the structure of equation (3) (p = 0 and q = 1) can be a mixture of different structures. Preferred structures are mixtures of 4,4-linked and 2,4-linked structures, and optionally 2,2-linked structures. Furthermore, preferred structures are mixtures in which at least 80 mol% of the structure has 4,4-linked connections and the remainder has 2,4-linked or 2,2-linked connections.

[0069] In addition to the aliphatic diisocyanate of formula (IIa), one or more other diisocyanates may be used in method step (i). Preferably, the amount of the one or more other diisocyanates used in method step (i) is up to 95 mol%, more preferably up to 93 mol%, also preferably up to 90 mol%, also preferably up to 80 mol%, also preferably up to 70 mol%, also preferably up to 60 mol%, also preferably up to 50 mol%, also preferably up to 40 mol%, also preferably up to 30 mol%, also preferably up to 20 mol%, also preferably up to 10 mol%, most preferably up to 5 mol%, based on the at least one diisocyanate of formula (IIa).

[0070] The one or more other diisocyanates mentioned in method step (i) are preferably at least one diisocyanate of formula (Xi). OCN-R 7 -NCO (Xi), Each R 7 The meaning is shown in formula (IIi). Those skilled in the art can also derive particularly preferred diisocyanates based on the preferred method of formula (IIi) above.

[0071] In step (i) of the method of the present invention, a prepolymer is prepared. Preferably, the M of the prepolymer is... n The number-average molecular weight M is 200 to 3000 g / mol, more preferably 220 to 2000 g / mol, and most preferably 230 to 1660 g / mol. n The determination is preferably performed by gel permeation chromatography. The method described above according to the present invention is particularly preferred for this purpose.

[0072] Preferred prepolymers according to the invention for producing the thermoplastic poly(urethane-co-carbonate) of the present invention are urethane diol prepolymers having a structure factor as defined below, having a structure of formula (XX). Where each R in equation (XX) 1 Each of these is independently a group having 6 to 18 carbon atoms and containing at least one ring; this group is a cycloaliphatic or heterocycloaliphatic group. and Where each R in equation (XX) 2 Each of the above is an independent group having 6 to 18 carbon atoms and containing at least one ring, wherein the group is a cycloaliphatic or heterocycloaliphatic group, wherein the structure R 2 The connection to the nitrogen atom shown in structure (XX) is made through secondary or tertiary carbon atoms. Where m is the arithmetic mean of the repeating units and is a number between 1.7 and 5.0.

[0073] The prepolymer particularly preferred by the present invention is wherein R 1 It can be expressed by the following formula: In equations (1a) and (2a), the positions marked with an asterisk "*" represent the positions of the oxygen atoms shown in equation (XX). And R 2 Prepolymer represented by the following formula (3) In equation (3), the positions marked with an asterisk "*" represent the positions of the nitrogen atoms shown in equation (XX); In equation (3), each R 3 Each is independently either methyl or ethyl, p is 0, 1 or 2, and q is 0 or 1.

[0074] In step (i), at least one diol of formula (Ia) may be preloaded. In this case, the diisocyanate of formula (IIa) is then added completely or over a longer period of time. However, at least one diol of formula (Ia) and at least one diisocyanate of formula (IIa) may also be added to the reactor simultaneously. Step (i) is preferably carried out at a temperature range of 90°C to 200°C, more preferably 100°C to 180°C, more preferably 110°C to 150°C, and most preferably 115°C to 145°C. Since the reaction is exothermic, the temperature of the reaction mixture may be at least temporarily between 100°C and 200°C, more preferably 150°C to 195°C, and even more preferably 170°C to 190°C. Since the reaction is exothermic, it is preferred that the reaction be carried out under reverse cooling. If the reaction in step (i) has already been carried out in the presence of at least one diaryl carbonate, the temperature should preferably not be too high. This minimizes the reaction of the diaryl carbonate in step (ii) to the greatest extent possible. Preferably, the upper temperature limit in this case is 90°C to 180°C.

[0075] Method step (i) can be performed under normal pressure nitrogen. However, it can also be performed under reduced or increased pressure.

[0076] Method step (i) is preferably carried out for such a long time that all present diisocyanates have essentially reacted. This can be verified, for example, by measuring the NCO content.

[0077] During step (i), the viscosity of the mixture typically increases. It is advantageous to perform thorough mixing in step (i). In some cases, it may also be advantageous to carry out step (i) in the presence of a solvent. This is especially true when high-viscosity prepolymers are obtained (e.g., when isosorbide is used as the diol). For this purpose, aromatic hydrocarbons, particularly chlorobenzene, are preferred. It is preferable that no solvent is present in step (i). This eliminates the need for an additional solvent removal step.

[0078] Method step (i) can be carried out in the absence of a catalyst or in the presence of at least one catalyst. Preferably, method step (i) is carried out in the absence of a catalyst. If a catalyst is used in method step (i), carbamate catalysts known to those skilled in the art can be used. Particularly preferred catalysts are aliphatic tertiary amines (e.g., bis(dimethylaminoethyl) ether, pentamethyldiethylenetriamine), cyclic aliphatic tertiary amines (e.g., 1,4-diaza(2,2,2)bicyclooctane), aliphatic amino ethers (e.g., dimethylaminoethyl ether and N,N,N-trimethyl-N-hydroxyethyldiaminoethyl ether), cyclic aliphatic amino ethers (e.g., N-ethylmorpholine), aliphatic amidines, cyclic aliphatic amidines, ureas, urea derivatives (e.g., aminoalkylureas), especially (3-dimethylaminopropylamine)urea, and tin catalysts (e.g., monoalkyltin oxide, dialkyltin oxide, dialkyltin dilaurate, tin octoate).

[0079] Preferably, (A) urea, urea derivatives, and / or (B) the aforementioned amines and amino ethers can be used as catalysts, characterized in that the amines and amino ethers contain functional groups that react chemically with isocyanates. Preferably, the functional group is a hydroxyl, primary, or secondary amino group. These particularly preferred catalysts have the advantage of significantly reducing migration and emission behavior. Examples of particularly preferred catalysts include: (3-dimethylaminopropylamine)-urea, 1,1'-((3-(dimethylamino)propyl)imino)bis-2-propanol, N-[2-[2-(dimethylamino)ethoxy]ethyl]-N-methyl-1,3-propanediamine, and 3-dimethylaminopropylamine and their derivatives, as well as similar molecules, wherein the dimethylamino group is substituted with a pyrrolidinyl group according to WO 2022 / 112157 A1.

[0080] Particularly preferably, monobutyltin oxide and / or dibutyltin oxide are used as catalysts in method step (i).

[0081] If a catalyst is used in method step (i), the amount used is preferably from 1 ppm to 1000 ppm, particularly preferably from 30 to 500 ppm, and most preferably from 50 to 170 ppm, based on the mass of the diisocyanate used.

[0082] Within the scope of this invention, unless otherwise specified, ppb and ppm shall be understood as parts by weight.

[0083] The prepolymer obtained by method step (i) is (substantially) OH-terminated due to the specific ratio of diol to diisocyanate. Furthermore, due to the use of excess diol, unreacted aliphatic diol of formula (Ia) (or aliphatic diol of formula (X), if present) is usually present immediately after method step (i). The one or more diols may be present in method step (ii) or may be removed prior to the step.

[0084] One aspect of the method of the present invention is characterized in that, between method steps (i) and (ii), at least a portion of the unreacted aliphatic diol of formula (Ia) is removed from the prepolymer. If present, at least one other aliphatic diol, preferably an aliphatic diol of formula (X), may also be removed.

[0085] According to the present invention, a polymer with a glass transition temperature of at least 90°C is obtained by using both cyclic aliphatic diols and cyclic aliphatic diisocyanates. Furthermore, it has proven particularly advantageous to at least partially remove the remaining (unreacted) aliphatic diols (formulas (Ia) and optionally (X)) after method step (i). This allows for influencing and further increasing the glass transition temperature. This enables targeted adjustment of the value of the glass transition temperature. It always depends on the chemical properties of the diol and diisocyanate used. Those skilled in the art will understand how the presence or absence of the aforementioned repeating unit (IV) can be particularly influenced thereby. For example, if unreacted diols are still present in the prepolymer at the beginning of method step (ii), the thermoplastic poly(urethane-co-carbonate) of the present invention typically contains repeating units of formula (IV).

[0086] Preferably, unreacted aliphatic diols of formula (Ia) (and optionally aliphatic diols of formula (X)) are removed by, for example, distillation, precipitation, and / or a thin-film evaporator. Various methods for removing aliphatic diols of formula (Ia) are familiar to those skilled in the art.

[0087] In step (ii), the prepolymer obtained in step (i) is reacted with a diaryl carbonate in the presence of at least one catalyst. According to the invention, this diaryl carbonate is sometimes also referred to as a carbonyl source. Depending on whether at least partially unreacted diols of formula (Ia) and optionally (X) are still present in the prepolymer, these diols may also be reacted with the diaryl carbonate in step (ii).

[0088] According to the present invention, it has been found that using diaryl carbonates, particularly diphenyl carbonates, achieves a sufficiently high increase in molecular weight. However, experiments using dimethyl carbonate instead of diphenyl carbonate, while using comparable parameters in other respects, have shown that using such dialkyl carbonates does not yield a sufficient increase in molecular weight, thus preventing the production of the poly(urethane-co-carbonate) according to the present invention.

[0089] Preferably, the molar ratio of diaryl carbonate to the present OH groups is 1.2:1 to 0.95:1, more preferably 1.11:1 to 0.98:1, and most preferably 1.07:1 to 0.99:1 (the first number represents the diaryl carbonate, and the second number represents the present OH groups). They can be derived from the prepolymer of step (i) or optionally from unreacted diols and / or further diols. The OH groups in the prepolymer are preferably determined by measuring the OH value. However, they can also be determined by theoretical calculation.

[0090] According to the invention, it is possible that method steps (i) and (ii) cannot be completely separated from each other. For example, it is possible that the diaryl carbonate in method step (ii) and the catalyst used in method step (ii) are already present in method step (i). In this case, it is impossible to completely avoid the fact that the intended reaction of method step (ii) has already occurred in small amounts in method step (i). However, it can be minimized (see above, for example, by controlling the temperature). According to the invention, it is expected that the reaction of the OH group with the NCO group will occur first (method step (i)), and then the reaction of the OH group with the diaryl carbonate will occur (method step (ii)). Those skilled in the art can perform these intended reactions so that they occur primarily in the order described above.

[0091] Preferably, the prepolymer obtained in step (i) is not separated. This means that step (ii) is preferably performed immediately following step (i). If the diaryl carbonate and catalyst are already present in at least part of step (i), this can be achieved, for example, by increasing the temperature and applying a vacuum, as described above. Alternatively, it can also be achieved by adding the diaryl carbonate and / or the catalyst and increasing the temperature and applying a vacuum.

[0092] Step (ii) is preferably performed at a temperature of 180°C to 260°C, more preferably 215°C to 255°C, and most preferably 220°C to 250°C. This temperature is preferably the final temperature. According to the invention, the final temperature can be achieved by gradually increasing the temperature.

[0093] In the reaction of method step (ii), a condensation product is typically formed. To shift the reaction equilibrium, it is advantageous to apply a vacuum in method step (ii). The vacuum level in method step (ii) is preferably from 500 mbar to 0.01 mbar, more preferably from 200 mbar to 0.01 mbar, and even more preferably from 200 mbar to 0.1 mbar. Particularly preferably, the vacuum level is gradually reduced. Most preferably, the vacuum level in the final stage is from 10 mbar to 0.01 mbar.

[0094] A preferred feature of the method of the present invention is that at least one catalyst present in step (ii) is an ammonium salt, a phosphonium salt, or an organic base. Those skilled in the art can select a suitable catalyst based on the reactivity of the substance used.

[0095] Catalysts suitable for step (ii) include all inorganic or organic basic compounds, such as hydroxides, carbonates, halides, phenolates, diphenolates, alkoxides, enolates, fluorides, acetates, phosphates, hydrogen phosphates, borates, oxides, nitrogen bases, and phosphorus bases of lithium, sodium, potassium, cesium, magnesium, calcium, barium, yttrium, titanium, manganese, iron, zinc, tin, and bismuth. Examples include tetramethylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium fluoride, tetramethylammonium tetraphenylborate, tetraphenylphosphine fluoride, tetraphenylphosphonium tetraphenylborate, dimethyldiphenylammonium hydroxide, tetraethylammonium hydroxide, hexadecyltrimethylammonium tetraphenylborate, hexadecyltrimethylammonium phenolate, and 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 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-phenyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7,7'-hexenedi-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7,7'-decenedi-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7,7'-dodecylenedi-1,5,7-triazabicyclo[4.4.0]dec-5-ene, or phosphazenes, such as phosphazene base P1-t-Oct = tert-octyliminotris(dimethylamino)phosphine, phosphazene base P1-t-Butyl = tert-butyliminotris(dimethylamino)phosphine, BEMP = 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diaza-2-phosphine.

[0096] Phosphorus catalysts of formula (VIII) are particularly suitable: Where Ra, Rb, Rc, and Rd can be the same or different C1 to C2. 10 Alkyl, C6 to C 14 Aryl, C7 to C 15 arylalkyl or C5 to C6 cycloalkyl, preferably methyl or C6 to C6 cycloalkyl. 14 Aryl, especially methyl or phenyl, X - It can be an anion, such as hydroxide, sulfate, bisulfate, bicarbonate, carbonate, or halide ions, preferably chloride ions or alkoxy or aryloxy ions of the formula -OR, wherein R can be C6 to C6. 14 Aryl, C7 to C 15Arylalkyl or C5 to C6 cycloalkyl, preferably phenyl.

[0097] Particularly preferred catalysts include: monobutyltin oxide, dibutyltin oxide, lithium hydroxide, lithium acetate dihydrate, sodium acetate trihydrate, magnesium acetate tetrahydrate, manganese acetate tetrahydrate, zinc acetate, iron(II) acetate, cesium carbonate, tetraisopropyl orthotitanate, titanium 2-ethylhexanoate, bismuth tris(2-ethylhexanoate), and yttrium 2-ethylhexanoate. Monobutyltin oxide, dibutyltin oxide, zinc acetate, and tetraisopropyl orthotitanate are particularly preferred. Sodium methoxide is also preferred.

[0098] These catalysts are preferably in the form of 1×10 -6 Up to 1×10 -4 mol, more preferably 1×10 -5 Up to 5×10 -5 The amount used is based on 1 mol of all (one or more) diisocyanate components used. The amount of alkoxide used can be from 0.1 to 100 ppm, preferably from 0.5 to 50 ppm, more preferably from 1 to 30 ppm, based on the total starting materials ((one or more) diols + (one or more) diisocyanates + diaryl carbonates). Brief description of the attached diagram: Figure 1 GPC spectra of the prepolymer (Example 2b) based on CHDM and H12-MDI at a molar ratio of 2:1 (diol: diisocyanate) are plotted with molar mass on the x-axis. Figure 2 : A detailed schematic diagram of the GPC spectrum of the prepolymer (Example 2b) used to determine the arithmetic mean "m" of the repeating units of the prepolymer and the residual diol content; the labels A to G represent individual peaks that must therefore be considered separately from each other. Figure 3 GPC spectra of the prepolymer (Example 11) of TCD-DM and H12-MDI at a molar ratio of 10:1 (diol: diisocyanate) are plotted with molar mass on the x-axis. Figure 4 : A detailed schematic diagram of the GPC spectrum of the prepolymer (Example 11) used to determine the arithmetic mean "m" of the repeating units of the prepolymer and the residual diol content; the labels A to E represent individual peaks that must therefore be considered separately from each other. Figure 5 : Poly(urethane-co-carbonate) based on CHDM and H12-MDI in a molar ratio of 2:1 (diol: diisocyanate) (Example 21) 13 C-NMR spectrum, Figure 6: Poly(urethane-co-carbonate) based on TCD-DM and H12-MDI in a molar ratio of 2:1 (diol: diisocyanate) (Example 46) 13 C-NMR spectroscopy. Example

[0100] Materials used: Diol component (according to formula (Ia) according to the present invention) CHDM (1) 1,4-cyclohexanediethanol: cis-1,4-cyclohexanediethanol and trans-1,4-cyclohexanediethanol A mixture of alkyldiethanol, CAS: 105-08-8, 99%, Sigma Aldrich, Germany. Used directly without further purification trans-CHDM (1) trans-1,4-cyclohexanediethanol, CAS No.: 3236-48-4, 97.77%, China BLDpharm, used directly without further purification. TCD-DM (2) Tricyclic sebacol: a mixture of isomers, CAS: 26896-48-0, 96%, Germany Sigma Aldrich, used directly without further purification. Diol components (comparison) ISB Polysorb PS A: Isosorbide, CAS: 652-67-5, 99.8%, France Roquette Freres, used directly without further purification HD 1,6-Hexanediol, CAS: 629-11-8, 97%, Sigma Aldrich, Germany, unprocessed. One-step purification for direct use. Diisocyanate component (according to formula (IIa) according to the present invention) H12-MDI (3) 1,1'-Methylenebis(4-isocyanate cyclohexane): a mixture of isomers, CAS: 5124-30-1, Covestro AG, Germany, used directly without further purification. Diisocyanate component (as a comparison when it is the only diisocyanate component, or as an additional diisocyanate component according to the present invention) HDI (Hexamethylene Diisocyanate), CAS: 822-06-0, Covestro AG, Germany, unregistered. Further purification for direct use. IPDI isophorone diisocyanates: cis-isophorone diisocyanates and trans-isophorone diisocyanates A mixture of phorone diisocyanates, CAS: 4098-71-9, Covestro, Germany AG, used directly without further purification. MDI diphenylmethane-4,4'-diisocyanate, CAS: 101-68-8, Covestro, Germany AG, stored at 45°C, is used directly without further purification. TDI (Toluene-2,4-diisocyanate), CAS: 584-84-9, Covestro AG, Germany, uncertified. Further purification for direct use. carbonyl source DPC diphenyl carbonate, CAS: 102-09-0, Covestro AG, Germany, new before use. Fresh distillation, catalyst Kat1 Monobutyltin Oxide, CAS: 2273-43-0, TIB Chemicals AG, Germany, unregistered. Further purification for direct use. Kat2 TBD: 1,5,7-Triazabicyclo(4.4.0)dec-5-ene, CAS: 5807-14-7, 98%, Sigma Aldrich (Germany) - Used directly without further purification. solvent MCB monochlorobenzene, CAS: 108-90-7, Azelis, Germany, used directly without further purification.

[0101] Analysis method: GPC: The molar mass distribution was determined by Currenta GmbH & Co. OHG using gel permeation chromatography (GPC). Approximately 30 mg of sample was weighed and dissolved in THF with gentle shaking. The sample was then filtered through a 0.45 µm PTFE filter and determined using a suitable GPC system equipped with an SDV column. Calibration was performed using narrow-distribution polystyrene standards (e.g., ReadyCal Kit Polystyrene Low, nominal molecular weight 266-66000 Da) and adjusted according to the column and sample. THF was used as the mobile phase. Detection was performed using ultraviolet (UV) radiation and refractive index detector (RI). This general method is defined by Currenta GmbH & Co. OHG in AM 2011-0623701-09D, which is available upon request from Currenta.

[0102] Determine the arithmetic mean m of the repeating units and the amount of residual diol in the prepolymer of Example 2b. In the synthesis of prepolymers, the amount of the diol component is always in excess relative to the diisocyanate component. This results in the formation of oligomers with an arithmetic mean of repeating units of m (see, for example, Equation (III)), thus leaving a certain proportion of the diol component unreacted in the mixture (e.g., ...). Figure 1 (The GPC spectrum of Example 2b is shown). The following explanation uses Example 2b as an example to explain the determination of the arithmetic mean m of the repeating units and the amount of residual diol.

[0103] The prepolymer and remaining unreacted diol (wt%) were determined by GPC spectra plotted with elution volume as the x-axis. Each detected peak, if clearly distinguishable, was assigned to either the unreacted monomeric diol or oligomer based on its molecular weight. If peaks were not clearly separated (a common occurrence in long-chain oligomers), they were split at the valley between the two peaks until no more valleys were measured (e.g., ...). Figure 2 (GPC spectrum of Example 2b is shown).

[0104] From Example 2b Figure 2 In the GPC spectrum, the following area F (%) was obtained: A: Prepolymer with repeating unit m = 5 (F = 12.4%) (This obviously also includes oligomers with higher repeating units, but the value is artificially specified as "5", see above) B: Prepolymer with repeating unit m = 4 (F = 9.9%) C: Prepolymer with repeating unit m = 3 (F = 15.3%) D: Prepolymer with repeating unit m = 2 (F = 22.4%) E: Prepolymer with repeating unit m = 1 (F = 27.7%) F: Unknown (F = 0.3%) G: Residual diol CHDM (F = 12.0%) m is determined based on the weighted arithmetic mean.

[0105] F (prepolymer) = 87.7% It will be clear to those skilled in the art that when the excess of the diol component is low, the accuracy of m determination by GPC is low because, due to the low resolution, higher-order oligomers (m ≥ 5) are mixed together in the GPC spectrum.

[0106] It will be clear to those skilled in the art that as the diol component is in excess, m decreases and the proportion of unreacted monomeric diols increases, as shown in Example 11 below (see Example 11). Figure 3 ).

[0107] From Example 11 Figure 4 The following area F (%) was obtained from the GPC spectrum shown: A: Prepolymer with repeating unit m = 3 (F = 0.7%) B: Prepolymer with repeating unit m = 2 (F = 4.9%) C: Prepolymer with repeating unit m = 1 (F = 24.8%) D: Unknown (F = 0.9%) E: Residual diol TCD-DM (F = 68.7%) m is determined based on the weighted arithmetic mean.

[0108] F (prepolymer) = 30.4% DSC: The glass transition temperature (Tg) was determined by dynamic differential scanning calorimetry (DSC) under nitrogen atmosphere at a heating rate of 20 K / min, according to DIN EN ISO 11357-1:2009-10 and ISO 11357-2:2013-05 standards, at the inflection point of the second heating process.

[0109] 1 H-NMR spectroscopy: use 1 H-NMR spectroscopy can confirm that the diol and diisocyanate components are almost completely (>97%) incorporated into the polymer.

[0110] Determination of aromatic groups in poly(urethane-co-carbonate): pass 1 H-NMR spectroscopy was used to determine the proportion (aromaticity) of aromatic hydrocarbons in poly(urethane-co-carbonate) produced using aromatic diisocyanates (such as MDI and TDI). For this purpose, approximately 20 mg of sample was dissolved in a suitable solvent (chloroform-d1 or DMSO-d6) and measured at a frequency of 600.4 MHz on a Bruker AV III HD 600 NMR spectrometer.

[0111] Measurement parameters: Pulse program pulprog zg30 Number of incremental scans per NS: 64 Relaxation time D1 between two scans: 3 seconds In principle, poly(urethane-co-carbonate) based on partially aromatic diisocyanates (Examples 34-37) is considered to comprise a polyurethane portion made from aromatic diisocyanates and diols, a polyurethane portion derived from aliphatic diisocyanates and diols, and a polycarbonate portion made from diols. The aromaticity of the polyurethane portion made from aromatic diisocyanates and diols can be determined by measuring the molecular weight of the polyurethane repeating unit and the proportion of aromatic hydrocarbons it contains.

[0112] For poly(urethane-co-carbonate) based on CHDM, MDI, and H12-MDI (Examples 34 and 35), the integral value (also known as the area, abbreviated as F) of the chemical shift signal at 7.1 ppm was selected to identify polyurethanes made from MDI and CHDM, which can be attributed to the four CH protons in MDI. The integral value of the signal at 4.2–5.0 ppm was selected to identify polyurethanes made from H12-MDI and CHDM, which can be attributed to the two CH2 protons in H12-MDI. The integral value of the CH2 signal at 3.1–4.2 ppm was selected to identify polycarbonates made from CHDM, which, in addition to being attributed to the four CH2 protons on the carbonate functional groups, can also be attributed to the six CH2 protons of polyurethanes made from MDI and CHDM, and polyurethanes made from H12-MDI and CHDM, respectively. Therefore, in the case of the integrated value of the signal at 3.1-4.2 ppm, the proportional integrated value of 6 protons of each polyurethane must be subtracted to obtain the integrated value of 4 CH2 protons of polycarbonate made from CHDM.

[0113] The molar percentage of aromatic polyurethanes prepared from MDI and CHDM is calculated using the following formula: Using the molecular weight of the repeating unit (394.5 g / mol) and the molecular weight of the aromatic portion (152.2 g / mol) of the polyurethane prepared from MDI and CHDM, the proportion of aromatic groups in poly(urethane-co-carbonate) (Examples 34 and 35) based on the relative proportions of the aromatic polyurethane prepared from MDI and CHDM can be calculated according to the following formula: For poly(urethane-co-carbonate) made from CHDM, TDI, and H12-MDI (Examples 36 and 37), the integral value (also known as area, abbreviated as F) of the chemical shift signal at 2.2 ppm was selected to identify polyurethane made from MDI and CHDM, which can be attributed to the three CH3 protons in TDI. For the identification of polyurethane made from H12-MDI and CHDM, the integral value of the signal at 4.3–4.9 ppm was selected, which can be attributed to the two CH2 protons in H12-MDI. To identify polycarbonate made from CHDM, the integral value of the CH2 signal at 3.2–4.2 ppm was selected, which, in addition to being attributed to the four CH2 protons on the carbonate functional groups, can also be attributed to the four CH2 protons in polyurethane made from TDI and CHDM, as well as the four CH2 protons in H12-MDI. 12 Polyurethanes made from MDI and CHDM have 6 CH2 protons. Therefore, in the case of the integrated value of the signal at 3.1–4.2 ppm, the proportional integrated value of 4 or 6 protons in the respective polyurethanes must be subtracted to obtain the integrated value of 4 CH2 protons in the polycarbonate made from CHDM.

[0114] The molar percentage of aromatic polyurethanes prepared from TDI and CHDM is obtained using the following formula: Using the repeating unit molecular weight of 318.4 g / mol and the molecular weight of the aromatic portion contained therein of the polyurethane prepared from TDI and CHDM, the proportion of aromatic groups in the poly(urethane-co-carbonate) (Examples 36 and 37) based on CHDM, TDI and H12-MDI (Examples 36 and 37) can be calculated according to the following formula based on the relative proportions of the aromatic polyurethane prepared from TDI and CHDM: It will be clear to those skilled in the art that when using other aromatic diisocyanates different from MDI and TDI, and other diols different from CHDM, different signals must be used to identify the one or more polyurethanes and polycarbonates, thereby determining the aromaticity.

[0115] 13 C-NMR spectroscopy: pass 13 C-NMR was used to determine the ratio of urethane groups to carbonate groups in poly(urethane-co-carbonate). For this purpose, approximately 20 mg of sample was dissolved in a suitable solvent (chloroform-d1), and measurements were performed at a measurement frequency of 151 MHz on a Bruker AV III HD 600 NMR spectrometer.

[0116] Measurement parameters: Pulse program pulprog zgig30 Number of incremental scans per NS: 512 Relaxation time D1 between two scans: 4 The following illustrative example illustrates the evaluation of the urethane to carbonate group ratio in Example 21 of a poly(urethane-co-carbonate) prepared from 1,4-cyclohexanediethanol (CHDM) and H12-MDI in a used molar ratio of 2:1 (diol: diisocyanate). See also Figure 5 .

[0117] 13 C-NMR spectra are used to identify the relationship between carbamates and carbonates. Signal at 156 ppm for carbamate Signal at 155.5 ppm for carbonates The molar ratio is derived directly from the respective signal areas normalized to 100.

[0118] according to Figure 5 In 13 C-NMR spectroscopy yielded the following estimated molar ratio: Carbamate = 65 Carbonate = 35 The ratio of urethane to carbonate groups in Example 46 of poly(urethane-co-carbonate) based on tricyclodecanediethanol (TCD-DM) and H12-MDI in a molar ratio of 2:1 (diol: diisocyanate) was evaluated.

[0119] 13 C-NMR spectra are used to identify the relationship between carbamates and carbonates. The signal of carbamate at 156 ppm The signal of carbonate at 155.5 ppm The molar ratio is derived directly from the respective signal areas normalized to 100.

[0120] according to Figure 6 In 13 C-NMR spectroscopy yielded the following estimated molar ratio: Carbamate = 66 Carbonate = 34 Hydroxyl value: The hydroxyl value (also known as the OH value) was determined by Currenta GmbH & Co. OHG using a titration method according to DIN EN ISO 4629-2. However, the base used was pyridine, not N-methyl-2-pyrrolidone as used in DIN EN ISO 4629-2. The method used is defined in Currenta GmbH & Co. OHG number 2011-0232602-92D, which is available upon request from Currenta.

[0121] NCO value: The NCO content was determined by titration according to DIN EN ISO 11909:2007-05.

[0122] Production of urethane diol (UDO) as a precursor for poly(urethane-co-carbonate) (PUC) Example 1: In the presence of Kat1, CHDM (according to formula (1)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit in a molar ratio of 3:2 (diol: diisocyanate). 123.75 g (858 mmol) of CHDM and 0.015 g (100 ppm based on H12-MDI) of Kat1 were pre-loaded into a flask equipped with a reflux condenser and a dropping funnel. Under nitrogen protection, the mixture was melted and heated to 100 °C with stirring at atmospheric pressure. At 100 °C for 2 hours, 150 g (572 mmol) of H12-MDI was added dropwise through the dropping funnel. The temperature was then raised to 130 °C, and the mixture was stirred at 130 °C for 60 minutes. After 60 minutes, a sample was taken under countercurrent nitrogen for NCO determination. The reaction was terminated when the NCO value was 0%. A colorless prepolymer with an OH value of 118.3 mg KOH / g was obtained. n It is 1630 g / mol.

[0123] Example 2a: CHDM (according to formula (1)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit in a molar ratio of 2:1 (diol: diisocyanate). 660 g (4.58 mol) CHDM and 600 g (2.29 mol) H12-MDI were pre-loaded into a flask equipped with a reflux condenser. The mixture was melted under nitrogen protection and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 2 hours. After 2 hours, a sample was taken under countercurrent nitrogen for NCO determination. The reaction was terminated when the NCO value was 0%. A colorless prepolymer was obtained with an OH value of 207.7 mg KOH / g. n It is 830 g / mol.

[0124] Example 2b: In the presence of Kat1, CHDM (according to formula (1)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit in a molar ratio of 2:1 (diol: diisocyanate). 440 g (3.05 mol) CHDM and 0.04 g (100 ppm based on H12-MDI) Kat1 were pre-loaded into a flask equipped with a reflux condenser and a dropping funnel. Under nitrogen protection, the mixture was melted and heated to 130 °C with stirring at atmospheric pressure. At 130 °C for 3 hours, 400 g (1.525 mol) H12-MDI was added dropwise through the dropping funnel. The mixture was then stirred at 130 °C for another 4 hours. After 4 hours, a sample was taken under countercurrent nitrogen for NCO determination. The reaction was terminated when the NCO value was 0%. A colorless prepolymer with an OH value of 204.7 mg KOH / g was obtained. n It is 780 g / mol.

[0125] Example 3: CHDM (according to formula (1)) as the diol component and H12-MDI (according to formula (3)) as the diisocyanate structural unit are reacted in a molar ratio of 3:1 (diol: diisocyanate). 330 g (2.29 mol) CHDM and 200 g (0.762 mol) H12-MDI were pre-loaded into a flask equipped with a reflux condenser. The mixture was melted under nitrogen protection and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 2 hours. After 2 hours, a sample was taken under countercurrent nitrogen for NCO determination. The reaction was terminated when the NCO value was 0%. A colorless prepolymer was obtained with an OH value of 314.5 mg KOH / g. n It is 550 g / mol.

[0126] Example 4:In the presence of Kat1, CHDM (according to formula (1)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit at a molar ratio of 4:1 (diol: diisocyanate). 880 g (6.10 mol) CHDM and 0.040 g (100 ppm based on H12-MDI) Kat1 were pre-loaded into a flask equipped with a reflux condenser and a dropping funnel. Under nitrogen protection, the mixture was melted and heated to 100 °C with stirring at atmospheric pressure. At 100 °C for 4 hours, 400 g (1.52 mmol) H12-MDI was added dropwise through the dropping funnel. The temperature was then raised to 130 °C and stirred for 60 minutes. After 60 minutes, a sample was taken under countercurrent nitrogen for NCO determination. The reaction was terminated when the NCO value was 0%. A colorless prepolymer with an OH value of 384.5 mg KOH / g was obtained. n It is 460 g / mol.

[0127] Example 5: CHDM (according to formula (1)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit in a molar ratio of 10:1 (diol: diisocyanate). 550 g (4.58 mol) CHDM and 100 g (2.29 mol) H12-MDI were pre-loaded into a flask equipped with a reflux condenser. The mixture was melted under nitrogen protection 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 under countercurrent nitrogen for NCO determination. The reaction was terminated when the NCO value was 0%. A colorless prepolymer was obtained with an OH value of 588.9 mg KOH / g. n It is 300 g / mol.

[0128] Example 6: Trans-CHDM (according to formula (1)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit in a molar ratio of 2:1 (diol: diisocyanate). 50.0 g (0.35 mol) trans-CHDM and 45.45 g (0.17 mol) H12-MDI were pre-loaded into a flask equipped with a reflux condenser. The mixture was melted under nitrogen protection and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 2 hours. After 2 hours, a sample was taken under countercurrent nitrogen for NCO determination. The reaction was terminated when the NCO value was 0%. A colorless prepolymer was obtained with an OH value of 189.5 mg KOH / g and M... n It is 930 g / mol.

[0129] Example 7: TCD-DM (according to formula (2)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit in a molar ratio of 3:2 (diol: diisocyanate). 112 g (0.57 mol) TCD-DM and 100 g (2.29 mol) H12-MDI were pre-loaded into a flask equipped with a reflux condenser. The mixture was melted under nitrogen protection and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 2 hours. After 2 hours, a sample was taken under countercurrent nitrogen for NCO determination. The reaction was terminated when the NCO value was 0%. A colorless prepolymer was obtained with an OH value of 104.4 mg KOH / g. n It is 1200 g / mol.

[0130] Example 8: TCD-DM (according to formula (2)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit in a molar ratio of 2:1 (diol: diisocyanate). 300 g (1.53 mol) TCD-DM and 200 g (0.76 mol) H12-MDI were pre-loaded into a flask equipped with a reflux condenser. The mixture was melted under nitrogen protection and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 2 hours. After 2 hours, a sample was taken under countercurrent nitrogen for NCO determination. The reaction was terminated when the NCO value was 0%. A colorless prepolymer was obtained with an OH value of 170.9 mg KOH / g. n It is 750 g / mol.

[0131] Example 9: TCD-DM (according to formula (2)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit in a molar ratio of 3:1 (diol: diisocyanate). 157 g (0.80 mol) TCD-DM and 70 g (0.27 mol) H12-MDI were pre-loaded into a flask equipped with a reflux condenser. The mixture was melted under nitrogen protection and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 2 hours. After 2 hours, a sample was taken under countercurrent nitrogen for NCO determination. The reaction was terminated when the NCO value was 0%. A colorless prepolymer was obtained with an OH value of 263.0 mg KOH / g and M... n It is 420 g / mol.

[0132] Example 10:TCD-DM (according to formula (2)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit in a molar ratio of 4:1 (diol: diisocyanate). 150 g (0.76 mol) TCD-DM and 50 g (0.19 mol) H12-MDI were pre-loaded into a flask equipped with a reflux condenser. The mixture was melted under nitrogen protection and heated to 130 °C at atmospheric pressure. The mixture was stirred at 130 °C for 2 hours. After 2 hours, a sample was taken under countercurrent nitrogen for NCO determination. The reaction was terminated when the NCO value was 0%. A colorless prepolymer was obtained with an OH value of 321.0 mg KOH / g. n It is 330 g / mol.

[0133] Example 11: TCD-DM (according to formula (2)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit in a molar ratio of 10:1 (diol: diisocyanate). 500 g (2.55 mol) TCD-DM and 50 g (0.25 mol) H12-MDI were pre-loaded into a flask equipped with a reflux condenser. The mixture was melted under nitrogen protection and heated to 130 °C at atmospheric pressure. The mixture was stirred at 130 °C for 1 hour. After 1 hour, a sample was taken under countercurrent nitrogen for NCO determination. The reaction was terminated when the NCO value was 0%. A colorless prepolymer was obtained with an OH value of 448.8 mg KOH / g. n It is 230 g / mol.

[0134] Example 12: In the presence of Kat1, CHDM (according to formula (1)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit at a molar ratio of 2:1 (diol: diisocyanate), followed by distillation to remove excess CHDM. 440 g (3.05 mol) CHDM and 0.040 g (100 ppm based on H12-MDI) Kat1 were pre-loaded in a flask equipped with a reflux condenser and a dropping funnel. Under nitrogen protection, the mixture was melted and heated to 100 °C with stirring at atmospheric pressure. 400 g (1.52 mmol) H12-MDI was added dropwise through the dropping funnel over 3 hours at 130 °C. The temperature was then raised to 130 °C and stirred for 4 hours. The reaction was stopped, and the mixture was allowed to stand overnight in the flask. Distillation was performed the next day. For this purpose, the dropping funnel and reflux condenser were removed, and a Wiegler column with a distillation bridge was installed. The unreacted monomeric glycol CHDM was distilled under reduced pressure (<1 mbar) and a bath temperature of 180 °C. After distillation, a pale yellow prepolymer with an OH value of 137.7 mg KOH / g and M n It is 1130 g / mol.

[0135] Example 13: In the presence of Kat1, CHDM (according to formula (1)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit at a molar ratio of 3:1 (diol: diisocyanate), and then excess CHDM is removed by distillation. 330 g (2.29 mol) CHDM and 0.020 g (100 ppm based on H12-MDI) Kat1 were pre-loaded in a flask equipped with a reflux condenser and a dropping funnel. Under nitrogen protection, the mixture was melted and heated to 100 °C with stirring at atmospheric pressure. At 100 °C for 2 hours, 200 g (0.76 mmol) H12-MDI was added dropwise through the dropping funnel. The temperature was then raised to 130 °C and the mixture was stirred at 130 °C for 2 hours. After 2 hours, a sample was taken under countercurrent nitrogen for NCO determination. The NCO value was 0%. The reaction was stopped, and the mixture was allowed to stand overnight in the flask. Distillation was performed the next day. For this purpose, the dropping funnel and reflux condenser were removed, and a Wiegler column with a distillation bridge was installed. The unreacted monomeric diol CHDM was distilled under reduced pressure (<1 mbar) and at a bath temperature of 175 °C. After distillation, a pale yellow prepolymer was obtained with an OH value of 118.3 mg KOH / g. n It is 1660 g / mol.

[0136] Example 14: In the presence of Kat1, CHDM (according to formula (1)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit at a molar ratio of 4:1 (diol: diisocyanate), and then excess CHDM is removed by distillation. 440 g (3.05 mol) CHDM and 0.02 g (100 ppm based on H12-MDI) Kat1 were pre-loaded into a flask equipped with a reflux condenser and a dropping funnel. Under nitrogen protection, the mixture was melted and heated to 100 °C with stirring at atmospheric pressure. At 100 °C for 2 hours, 200 g (0.76 mmol) H12-MDI was added dropwise through the dropping funnel. The temperature was then raised to 130 °C, and the mixture was stirred at 130 °C for 2 hours. After 2 hours, a sample was taken under countercurrent nitrogen for NCO determination. The NCO value was 0%. The reaction was stopped, and the mixture was allowed to stand overnight in the flask. Distillation was performed the next day. For this purpose, the dropping funnel and reflux condenser were removed, and a Wiegler column with a distillation bridge was installed. The unreacted monomeric diol CHDM was distilled under reduced pressure (<1 mbar) and a bath temperature of 175 °C. After distillation, a pale yellow prepolymer was obtained with an OH value of 141.5 mg KOH / g. n It is 1330 g / mol.

[0137] Example 15: In the presence of Kat1, CHDM (according to formula (1)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit at a molar ratio of 10:1 (diol: diisocyanate), and then excess CHDM is removed by distillation. 550 g (3.81 mol) CHDM and 0.01 g (100 ppm based on H12-MDI) Kat1 were pre-loaded into a flask equipped with a reflux condenser and a dropping funnel. Under nitrogen protection, the mixture was melted and heated to 100 °C with stirring at atmospheric pressure. At 100 °C for 3 hours, 100 g (0.38 mmol) H12-MDI was added dropwise through the dropping funnel. The temperature was then raised to 130 °C, and the mixture was stirred at 130 °C for 1 hour. After 1 hour, a sample was taken under countercurrent nitrogen for NCO determination. The NCO value was 0%. The reaction was stopped, and the mixture was allowed to stand overnight in the flask. Distillation was performed the next day. For this purpose, the dropping funnel and reflux condenser were removed, and a Wiegler column with a distillation bridge was installed. The unreacted monomeric diol CHDM was distilled under reduced pressure (<1 mbar) and a bath temperature of 200 °C. After distillation, a pale yellow prepolymer was obtained with an OH value of 216.7 mg KOH / g. n It is 640 g / mol.

[0138] Table 1: Comparison of results from Examples 1 to 15 UDO (urethane diol) produced from aromatic diisocyanates is used as a precursor for poly(urethane-co-carbonate) (PUC). Example 16: CHDM (according to formula (1)) as the diol component reacts with H12-MDI (according to formula (3), A) and MDI (B) as diisocyanate structural units in a weight ratio of 9:1 at a molar ratio of 2:1 (diol: diisocyanate A+B). 110.5 g (0.77 mol) CHDM, 90 g (0.34 mol) H12-MDI, and 10 g (0.04 mol) MDI were pre-loaded into a flask equipped with a reflux condenser. The mixture was melted under nitrogen protection and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 1 hour. After 1 hour, a sample was taken under countercurrent nitrogen for NCO determination. The reaction was terminated when the NCO value was 0%. A pale yellow prepolymer was obtained with an OH value of 192.3 mg KOH / g and MDI. n It is 820 g / mol.

[0139] Example 17: CHDM (according to formula (1)) as the diol component reacts with H12-MDI (according to formula (3), A) and MDI (B) as diisocyanate structural units in a 1:1 weight ratio at a molar ratio of 2:1 (diol: diisocyanate A+B). 59.85 g (0.41 mol) CHDM, 25 g (0.10 mol) H12-MDI, and 25 g (0.11 mol) MDI were pre-loaded into a flask equipped with a reflux condenser. The mixture was melted under nitrogen protection and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 1 hour. After 1 hour, a sample was taken under countercurrent nitrogen for NCO determination. The reaction was terminated when the NCO value was 0%. A pale yellow prepolymer was obtained with an OH value of 210.9 mg KOH / g and MDI. n It is 790 g / mol.

[0140] Example 18: CHDM (according to formula (1)) as the diol component reacts with H12-MDI (according to formula (3), A) and TDI (B) as diisocyanate structural units in a weight ratio of 9:1 at a molar ratio of 2:1 (diol: diisocyanate A+B). 115.5 g (0.80 mol) CHDM, 90 g (0.34 mol) H12-MDI, and 10 g (0.06 mol) TDI were pre-loaded into a flask equipped with a reflux condenser. The mixture was melted under nitrogen protection and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 1 hour. After 1 hour, a sample was taken under countercurrent nitrogen for NCO determination. The reaction was terminated when the NCO value was 0%. A pale yellow prepolymer was obtained with an OH value of 198.8 mg KOH / g. n It is 750 g / mol.

[0141] Example 19: CHDM (according to formula (1)) as the diol component reacts with H12-MDI (according to formula (3), A) and TDI (B) as diisocyanate structural units in a 1:1 weight ratio at a molar ratio of 2:1 (diol: diisocyanate A+B). 137.8 g (0.96 mol) CHDM, 50 g (0.19 mol) H12-MDI, and 50 g (0.29 mol) TDI were pre-loaded into a flask equipped with a reflux condenser. The mixture was melted under nitrogen protection and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 1 hour. After 1 hour, a sample was taken under countercurrent nitrogen for NCO determination. The reaction was terminated when the NCO value was 0%. A pale yellow prepolymer was obtained with an OH value of 206.8 mg KOH / g. n It is 740 g / mol.

[0142] Table 2: Comparison of results from Examples 16 to 19 Example Diisocyanate A: Diisocyanate B (mass ratio) CHDM: Diisocyanate (A+B) (molar ratio) OH value (mg KOH / g) <![CDATA[M n (g / mol)]]> 16 H12-MDI:MDI (9:1) 2:1 192.3 820 17 H12-MDI:MDI (1:1) 2:1 210.9 790 18 H12-MDI:TDI (9:1) 2:1 198.8 750 19 H12-MDI:TDI (1:1) 2:1 206.8 740

[0143] Poly(urethane) is produced by the condensation polymerization of pre-prepared urethane diol (UDO) and diphenyl carbonate (DPC). Ester-co-carbonate)(PUC) Example 20: In the presence of Kat1, Example 1, as the UDO component, reacted with DPC as the carbonyl source at a molar ratio of 1:1 (UDO:DPC). 75.0 g (79.1 mmol) of Example 1 (OH value: 118.3 mg KOH / g), 16.94 g (79.1 mmol) of DPC, and 0.002 g (22 ppm based on the starting materials from Example 1 and DPC) of Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. The mixture was melted under nitrogen protection and heated to 150 °C with stirring at atmospheric pressure. The mixture was stirred at 150 °C for 30 minutes, then at 190 °C for 20 minutes. A vacuum was then applied. The pressure was reduced to 100 mbar over 10 minutes. Phenol was continuously removed during this period. Stirring continued at 100 mbar for approximately 60 minutes. Subsequently, the bath temperature was increased to 220 °C in 10 °C increments with 10-minute holding stages. The pressure was then reduced to <1 mbar (approximately 0.4 mbar), and condensation continued for 60 minutes. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 72600 g / mol.

[0144] Example 21: In the presence of Kat1, Example 2a reacted with DPC as the carbonyl source at a molar ratio of 1:1.03 (UDO:DPC) as the UDO component. 150.0 g (277.6 mmol) of Example 2a (OH value: 207.7 mg KOH / g), 61.34 g (286.3 mmol) of DPC, and 0.008 g (38 ppm based on the raw materials from Example 2a and DPC) of Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. Under nitrogen protection, the mixture was melted and heated to 150°C with stirring at atmospheric pressure. The mixture was stirred at 150°C for 30 minutes, then at 180°C for 20 minutes. Subsequently, a vacuum was applied to continuously remove the phenol. For this purpose, the pressure was reduced to 100 mbar over 10 minutes. The mixture was stirred at 180°C for 30 minutes, at 190°C for 30 minutes, at 200°C for 30 minutes, at 210°C for 10 minutes, at 220°C for 10 minutes, and at 240°C for 20 minutes. The pressure was then reduced to <1 mbar (approximately 0.6 mbar), and condensation continued for 60 minutes. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 86,700 g / mol.

[0145] Example 22: In the presence of Kat1, Example 2b, as the UDO component, was reacted by adding 0.5 equivalents of CHDM (according to formula (1)) and DPC as the carbonyl source in a 1:1 molar ratio ((UDO + 0.5 equivalents of CHDM): DPC). 75.0 g (137.2 mmol) of another batch of Example 2b (OH value: 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 feedstocks Example 2b, CHDM, and DPC) of Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. Under nitrogen protection, the mixture was melted and heated to 150°C with stirring at atmospheric pressure. The mixture was stirred at 150°C for 30 minutes, then at 190°C for 25 minutes. Subsequently, a vacuum was applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 20 minutes. The mixture was stirred at 190°C for 20 minutes, then the pressure was further reduced to <1 mbar (approximately 0.6 mbar) over 20 minutes, and condensation continued for 60 minutes. Then, the mixture was stirred at 220°C under high vacuum (approximately 0.4 mbar) for 4 hours. Afterward, the reaction was stopped. M was obtained. w It is a pale yellow polymer with a concentration of 92,700 g / mol.

[0146] Example 23: In the presence of Kat1, Example 2b, as the UDO component, was reacted by adding 1.0 equivalent of CHDM (according to formula (1)) and DPC as the carbonyl source in a 1:1 molar ratio ((UDO + 1.0 equivalent of CHDM): DPC). 75.0 g (137.2 mmol) of another batch of Example 2b (OH value: 205.3 mg KOH / 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 feedstocks Example 2b, CHDM, and DPC) of Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. Under nitrogen protection, the mixture was melted and heated to 160°C with stirring at atmospheric pressure. The mixture was stirred at 160°C for 30 minutes, then at 190°C for 20 minutes. 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 at 190°C for 30 minutes, then the pressure was further reduced to <1 mbar (approximately 0.8 mbar) over 10 minutes. It was then stirred at 220°C under high vacuum (approximately 0.4 mbar) for 4 hours. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 190,800 g / mol.

[0147] Example 24:In the presence of Kat1, Example 2b, as the UDO component, was reacted by adding 1.5 equivalents of CHDM (according to formula (1)) and DPC as the carbonyl source in a 1:1 molar ratio ((UDO + 1.5 equivalents of CHDM): DPC). 75.0 g (137.2 mmol) of another batch of Example 2b (OH value: 205.3 mg KOH / 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 feedstocks Example 2b, CHDM, and DPC) of Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. Under nitrogen protection, the mixture was melted and heated to 150°C with stirring at atmospheric pressure. The mixture was stirred at 150°C for 20 minutes, then at 190°C for 20 minutes. Subsequently, a vacuum was applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 20 minutes. The mixture was stirred at 190°C for 60 minutes, at 200°C for 10 minutes, and at 220°C for 20 minutes. The pressure was then reduced to <1 mbar (approximately 0.6 mbar), and condensation continued for 4 hours. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 250-300 g / mol.

[0148] Example 25: In the presence of Kat1, Example 2b, as the UDO component, was reacted by adding 2.0 equivalents of CHDM (according to formula (1)) and DPC as the carbonyl source in a 1:1 molar ratio ((UDO + 2.0 equivalents of CHDM): DPC). 75.0 g (137.2 mmol) of another batch of Example 2b (OH value: 205.3 mg KOH / 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 feedstocks Example 2b, CHDM, and DPC) of Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. Under nitrogen protection, the mixture was melted and heated to 150°C with stirring at atmospheric pressure. The mixture was stirred at 160°C for 30 minutes, then at 190°C for 20 minutes. 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 at 190°C for 30 minutes, then the pressure was further reduced to <1 mbar (approximately 0.9 mbar) over 20 minutes. Subsequently, it was stirred at 220°C under high vacuum (approximately 0.7 mbar) for 4 hours. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 122100 g / mol.

[0149] Example 26: In the presence of Kat1, Example 3 reacted UDO as the UDO component with DPC as the carbonyl source in a 1:1 molar ratio (UDO:DPC). 75.0 g (210.2 mmol) of Example 3 (OH value: 314.5 mg KOH / g), 45.03 g (210.2 mmol) of DPC, and 0.006 g (50 ppm based on starting material Example 3 and DPC) of Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. The mixture was melted under nitrogen protection and heated to 150°C with stirring at atmospheric pressure. The mixture was stirred at 150°C for 10 minutes, then at 180°C for 20 minutes. 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 at 180°C for 60 minutes, at 200°C for 10 minutes, and then at 220°C for 10 minutes. The pressure was then reduced to <1 mbar (approximately 0.4 mbar), and condensation continued for 4 hours. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 52,700 g / mol.

[0150] Example 27: In the presence of Kat1, Example 4 involved the reaction of UDO as the UDO component with DPC as the carbonyl source at a molar ratio of 1:1 (UDO:DPC). 75.0 g (257.0 mmol) of Example 4 (OH value: 384.5 mg KOH / g), 55.05 g (257.0 mmol) of DPC, and 0.007 g (54 ppm based on the starting material Example 4 and DPC) of Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. Under nitrogen protection, the mixture was melted and heated to 150°C with stirring at atmospheric pressure. The mixture was stirred at 150°C for 20 minutes, then at 190°C for 20 minutes. Subsequently, a vacuum was applied to continuously remove phenol. For this purpose, the pressure was reduced to 500 mbar over 10 minutes. The mixture was stirred at 190°C for 30 minutes, then 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 (approximately 0.3 mbar), and the mixture was further condensed for 4 hours. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 78200 g / mol.

[0151] Example 28: In the presence of Kat1, Example 5 involved the reaction of UDO as the UDO component with DPC as the carbonyl source at a molar ratio of 1:1 (UDO:DPC). 75.0 g (393.6 mmol) of Example 5 (OH value: 588.9 mg KOH / g), 82.0 g (382.8 mmol) of DPC, and 0.011 g (70 ppm based on starting material Example 5 and DPC) of Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. The mixture was melted under nitrogen protection and heated to 150°C with stirring at atmospheric pressure. The mixture was stirred at 150°C for 20 minutes, then at 190°C for 20 minutes. Subsequently, a vacuum was applied to continuously remove phenol. For this purpose, the pressure was reduced to 800 mbar over 10 minutes. The mixture was stirred at 190°C for 30 minutes, then 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 (approximately 0.3 mbar), and the mixture was further condensed for 4 hours. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 52,000 g / mol.

[0152] Example 29: In the presence of Kat1, Example 6 reacted UDO as the UDO component with DPC as the carbonyl source in a 1:1 molar ratio (UDO:DPC). 75.0 g (126.7 mmol) of Example 6 (OH value: 189.5 mg KOH / g), 27.13 g (126.6 mmol) of DPC, and 0.004 g (39 ppm based on the starting material Example 6 and DPC) of Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. Under nitrogen protection, the mixture was melted and heated to 150°C with stirring at atmospheric pressure. The mixture was stirred at 150°C for 20 minutes, then at 180°C for 20 minutes. 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 at 180°C for 30 minutes, at 190°C for 40 minutes, at 200°C for 20 minutes, at 210°C for 20 minutes, and at 220°C for 20 minutes. The pressure was then reduced to <1 mbar (approximately 0.4 mbar), and the mixture was allowed to condense for another 4 hours. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 50300 g / mol.

[0153] Example 30: In the presence of Kat1, Example 12 reacted with DPC as the carbonyl source in a 1:1 molar ratio (UDO:DPC) as the UDO component. 150.0 g (184.1 mmol) of Example 12 (OH value: 137.7 mg KOH / g), 39.43 g (184.1 mmol) of DPC, and 0.007 g (37 ppm based on the starting materials Example 12 and DPC) of Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. The mixture was melted under nitrogen protection and heated to 160 °C with stirring at atmospheric pressure. The mixture was stirred at 160 °C for 20 minutes, and then stirred again at 190 °C for 20 minutes. Subsequently, a vacuum was 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 at 220 °C for 30 minutes. The pressure was then reduced to <1 mbar (approximately 0.4 mbar), and the mixture was continued to condense for 2 hours. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 68,300 g / mol.

[0154] Example 31: In the presence of Kat1, Example 13 reacted with DPC as the carbonyl source in a 1:1 molar ratio (UDO:DPC) as the UDO component. 75.0 g (79.1 mmol) of Example 13 (OH value: 118.3 mg KOH / g), 16.94 g (79.1 mmol) of DPC, and 0.002 g (22 ppm based on the starting material Example 13 and DPC) of Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. The mixture was melted under nitrogen protection and heated to 160°C with stirring at atmospheric pressure. The mixture was stirred at 160°C for 10 minutes, then at 190°C for 20 minutes. 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 at 190°C for 60 minutes, then at 220°C for 10 minutes. The pressure was then reduced to <1 mbar (approximately 0.3 mbar) over 10 minutes, and the mixture was continued to condense for 60 minutes. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 93,300 g / mol.

[0155] Example 32: In the presence of Kat1, Example 14 reacted with DPC as the carbonyl source in a 1:1 molar ratio (UDO:DPC) as the UDO component. 75.0 g (94.6 mmol) of Example 14 (OH value: 141.5 mg KOH / g), 20.26 g (94.6 mmol) of DPC, and 0.003 g (31 ppm based on starting material Example 14 and DPC) of Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. The mixture was melted under nitrogen protection and heated to 150°C with stirring at atmospheric pressure. The mixture was stirred at 150°C for 15 minutes, then at 190°C for 20 minutes. Subsequently, a vacuum was 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 (approximately 0.4 mbar) over 15 minutes, and the mixture was further condensed for 60 minutes. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 80,500 g / mol.

[0156] Example 33: In the presence of Kat1, Example 15 reacted with DPC as the carbonyl source in a 1:1 molar ratio (UDO:DPC) as the UDO component. 150.0 g (289.7 mmol) of Example 15 (OH value: 216.7 mg KOH / g), 62.05 g (289.7 mmol) of DPC, and 0.007 g (33 ppm based on the starting material Example 15 and DPC) of Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. The mixture was melted under nitrogen protection and stirred and heated to 150 °C at atmospheric pressure. The mixture was stirred at 150 °C for 10 minutes, then at 190 °C for 20 minutes. A vacuum was then applied to continuously remove phenol. For this purpose, the pressure was reduced to <1 mbar (approximately 0.3 mbar) over 30 minutes. The mixture was heated to 210 °C over 30 minutes and condensation continued for 4 hours. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 30,300 g / mol.

[0157] Example 34: In the presence of Kat1, Example 16 was reacted with DPC as the carbonyl source at a molar ratio of 1:1.11 (UDO:DPC). 150.0 g (257.1 mmol) of Example 16 (OH value: 192.3 mg KOH / g), 61.4 g (286.6 mmol) of DPC, and 0.008 g (38 ppm based on starting material Example 16 and DPC) of Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. Under nitrogen protection, the mixture was melted and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 50 min, then at 180 °C for 20 min. A vacuum was then applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 15 min. The mixture was then gradually heated to 240 °C over 90 min. The pressure was then reduced to <1 mbar (approximately 0.5 mbar), and the mixture was continued to condense for 60 min. The reaction was then stopped. M was obtained. w It is a yellow polymer with a concentration of 73,800 g / mol.

[0158] Example 35: In the presence of Kat1, Example 17 was reacted with DPC as the carbonyl source at a molar ratio of 1:1.03 (UDO:DPC) as the UDO component. 75.0 g (141 mmol) of Example 17 (OH value: 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 Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. Under nitrogen protection, the mixture was melted and heated to 130°C with stirring at atmospheric pressure. The mixture was stirred at 130°C for 5 minutes, at 140°C for 5 minutes, and at 180°C for 20 minutes. A vacuum was then applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 5 minutes. Subsequently, the mixture was gradually heated to 240°C over 105 minutes. The pressure was then reduced to <1 mbar (approximately 0.2 mbar), and the mixture was continued to condense for 90 minutes. The reaction was then stopped. M was obtained. w It is a yellow polymer with a concentration of 127,900 g / mol.

[0159] Example 36: In the presence of Kat1, Example 18 was reacted with DPC as the carbonyl source at a molar ratio of 1:1.10 (UDO:DPC). 75.0 g (132.9 mmol) of Example 18 (OH value: 198.8 mg KOH / g), 31.3 g (146.1 mmol) of DPC, and 0.004 g (38 ppm based on the starting material Example 18 and DPC) of Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. Under nitrogen protection, the mixture was melted and heated to 130°C with stirring at atmospheric pressure. The mixture was stirred at 130°C for 20 minutes, then 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 30 minutes. The mixture was then gradually heated to 240°C over 60 minutes. The pressure was then reduced to <1 mbar (approximately 0.9 mbar), and the mixture was continued to condense for 60 minutes. The reaction was then stopped. M was obtained. w It is a yellow polymer with a concentration of 79,600 g / mol.

[0160] Example 37: In the presence of Kat1, Example 19 was reacted with DPC as the carbonyl source at a molar ratio of 1:1.14 (UDO:DPC). 75.0 g (138.2 mmol) of Example 19 (OH value: 206.8 mg KOH / g), 33.9 g (158.2 mmol) of DPC, and 0.004 g (37 ppm based on the starting material Example 19 and DPC) of Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. Under nitrogen protection, the mixture was melted and heated to 130°C with stirring at atmospheric pressure. The mixture was stirred at 130°C for 15 minutes, then at 180°C for 20 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 then gradually heated to 240°C over 70 minutes. The pressure was then reduced to <1 mbar (approximately 0.5 mbar), and the mixture was continued to condense for 60 minutes. The reaction was then stopped. M was obtained. w It is a yellow polymer with a concentration of 43,300 g / mol.

[0161] Table 3: Comparison of results from Examples 20 to 37 Example 1* UDO (urethane diol) <![CDATA[M w (g / mol)]]> Tg (°C) Molar ratio (carbonate:carbamate) Aroma degree (molar %) impression** 20 E Example 1 72600 121 19:81 - ductility 21 E Example 2a 86700 111 35:65 - ductility 22 E Example 2b + 0.5 equivalent CHDM 92700 106 38:62 - ductility 23 E Example 2b + 1.0 Eq CHDM 190800 100 49:51 - ductility 24 E Example 2b + 1.5 equivalent CHDM 250300 92 56:44 - ductility 25 V Example 2b + 2.0 Eq CHDM 122100 88 59:41 - ductility 26 E Example 3 52700 97 45:55 - ductility 27 V Example 4 78200 89 58:42 - ductility 28 V Example 5 52000 66 81:19 - ductility 29 E Example 6 50300 113 30:70 - ductility 30 E Example 12 68300 119 22:78 - ductility 31 E Example 13 93300 122 20:80 - ductility 32 E Example 14 80500 118 23:77 - ductility 33 V Example 15 30300 106 27:73 - brittleness 34 E Example 16 73800 103 30:70 2 ductility 35 E Example 17 127900 109 35:65 10 ductility 36 E Example 18 79600 110 33:67 2 ductility 37 E Example 19 43300 107 38:62 7 ductility * E represents the present invention, V represents the comparative example. A preliminary impression can be obtained by manually bending a solidified melt. If it does not break when bent, the material is described as "ductile"; otherwise, it is described as "brittle".

[0162] Production of poly(urethane-co-carbonate) (PUC) - One-pot process Example 38:In the presence of Kat1, CHDM (according to formula (1)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit and DPC as the carbonyl source in a molar ratio of 2:1:1.05 (diol: diisocyanate: DPC). 110 g (0.76 mol) CHDM, 100 g (0.38 mol) H12-MDI, 86.0 g (0.40 mol) DPC, and 0.01 g (34 ppm based on the starting materials CHDM, H12-MDI, and DPC) Kat1 were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. Under nitrogen protection, the mixture was melted and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 1 hour. 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 hours. The mixture was stirred at 240 °C for 20 minutes. The pressure was then reduced to <1 mbar (approximately 0.2 mbar) over 60 minutes, and the mixture was further condensed for 1 hour. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 61,000 g / mol.

[0163] Production of poly(aminobenzoic acid ester-co-carbonate) (PUC) – Sequential One-Pot Process Example 39: In the presence of Kat1, CHDM (according to formula (1)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit, and then reacts with DPC as the carbonyl source, wherein the molar ratio is 2:1:1.05 (diol: diisocyanate: DPC). 220 g (1.53 mol) CHDM, 200 g (0.76 mol) H12-MDI, and 0.02 g (48 ppm based on raw materials CHDM and H12-MDI) Kat1 were pre-loaded into a flask equipped with a Wiegler column and distillation bridge. The mixture was melted under nitrogen protection and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 1 hour. After 1 hour, a sample was taken under countercurrent nitrogen for NCO measurement. The NCO value was 0%. After continuing stirring under countercurrent nitrogen for 30 minutes, 163.7 g (0.76 mol) DPC was added. The mixture was heated to 180 °C and stirred at 180 °C for 20 minutes. Subsequently, a vacuum was 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 80 minutes. The mixture was stirred at 220 °C for 10 minutes. The pressure was then reduced to <1 mbar (approximately 0.2 mbar) over 35 minutes, and the mixture continued to condense for 4 hours. The reaction was then stopped. M was obtained.w It is a pale yellow polymer with a concentration of 68,800 g / mol.

[0164] Example 40: In the presence of Kat1, CHDM (according to formula (1)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit, and then reacts with DPC as the carbonyl source, wherein the molar ratio is 2:1:1 (diol: diisocyanate: DPC). 220 g (1.53 mol) CHDM and 200 g (0.76 mol) H12-MDI were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. The mixture was melted under nitrogen protection and heated to 130 °C with stirring at atmospheric pressure. The mixture was stirred at 130 °C for 2 hours. After 2 hours, 163.7 g (0.76 mol) DPC and 0.02 g (34 ppm based on the feed CHDM, H12-MDI, and DPC) Kat1 were added under countercurrent nitrogen. The mixture was heated to 180 °C and stirred at 180 °C for 20 min. Subsequently, a vacuum was applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 10 min, and the bath temperature was increased to 220 °C over 10 min. The mixture was stirred at 220 °C for 45 min. Then, the pressure was reduced to <1 mbar (approximately 0.4 mbar) over 35 min, and the mixture was further condensed for 2 hours. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 114,700 g / mol.

[0165] Example 41: In the presence of Kat1, ISB as a diol component (comparative) reacts with H12-MDI (according to formula (3)) as a diisocyanate structural unit, and then reacts with Kat2 and DPC as carbonyl sources, wherein the molar ratio is 2:1:1 (diol: diisocyanate: DPC). 167.3 g (1.14 mol) of ISB and 0.017 g (113 ppm based on H12-MDI) of Kat1 were pre-loaded into a flask equipped with a reflux condenser and a dropping funnel. Under nitrogen protection, the mixture was melted and heated to 100 °C with stirring at atmospheric pressure. Over 2 hours, 150 g (0.57 mol) of H12-MDI was added dropwise through the dropping funnel. The temperature was then raised to 150 °C, and the mixture was stirred at 150 °C for 4 hours. After 4 hours, a sample was taken under countercurrent nitrogen for NCO determination. The NCO value was 0%. The reaction was stopped and allowed to stand overnight in the flask. Polycondensation was carried out the next day. For this, the dropping funnel and reflux condenser were removed, and a Wiegler column with a distillation bridge was installed. The mixture was melted under nitrogen protection and heated to 180 °C with stirring at atmospheric pressure. 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 under countercurrent nitrogen. The mixture was heated to 200 °C and stirred for 30 minutes. A vacuum was then applied to continuously remove phenol. To do this, the pressure was reduced to <1 mbar (approximately 0.4 mbar) over 100 minutes, and the bath temperature was gradually increased to 240 °C. The mixture continued to condense at 240 °C for 4 hours. The reaction was then stopped. M was obtained. w It is a dark brown polymer with a concentration of 16600 g / mol.

[0166] Example 42: In the presence of Kat1, HD as a diol component (comparative) reacts with H12-MDI (according to formula (3)) as a diisocyanate structural unit, and then reacts by adding Kat1 again with DPC as a carbonyl source, wherein the molar ratio is 2:1:1 (diol: diisocyanate: DPC). 47.47 g (402 mmol) HD, 0.003 g (57 ppm based on H12-MDI) Kat1, and 100 g MCB were pre-loaded into a flask equipped with a reflux condenser and a dropping funnel. Under nitrogen protection, the mixture was stirred and heated to 120 °C at atmospheric pressure. Over 20 minutes, 52.63 g (201 mmol) H12-MDI was added dropwise through the dropping funnel. The mixture was then stirred at 120 °C for 2 hours. After 2 hours, a sample was taken under countercurrent nitrogen for NCO determination. The NCO value was 0%. The reaction was stopped and allowed to stand overnight in the flask. Polycondensation was carried out the next day. For this, the dropping funnel and reflux condenser were removed, and a Wiegler column with a distillation bridge was installed. 43.16 g (201 mmol) DPC and 0.005 g (105 ppm based on HD) Kat1 were added to the mixture. Under nitrogen protection, the mixture was stirred and heated to 170°C at atmospheric pressure for 20 minutes. A vacuum was then applied to continuously remove MCB and phenol. For this purpose, 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 continued to condense at 220°C for 4 hours. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 80900 g / mol.

[0167] Example 43: In the presence of Kat1, CHDM (according to formula (1)) as the diol component reacts with IPDI as the diisocyanate structural unit (comparative), and then reacts by adding Kat1 again with DPC as the carbonyl source, wherein the molar ratio is 2:1:1 (diol: diisocyanate: DPC). 168 g (1.16 mol) CHDM, 0.017 g (131 ppm based on IPDI) Kat1, and 162 g MCB were pre-loaded into a flask equipped with a reflux condenser and a dropping funnel. Under nitrogen protection, the mixture was stirred and heated to 120 °C at atmospheric pressure. Over 75 minutes, 129.5 g (0.58 mol) IPDI was added dropwise through the dropping funnel. The mixture was then stirred at 120 °C for 4 hours. After 4 hours, NCO was measured under countercurrent nitrogen. The NCO value was 0%. The reaction was stopped and allowed to stand in the flask for two nights. Polycondensation was then carried out after two days. For this purpose, the dropping funnel and reflux condenser were removed, and a Wiegler column with a distillation bridge was installed. 124.8 g (0.58 mol) DPC and 0.017 g (131 ppm based on IPDI) Kat1 were added to the mixture. Under nitrogen protection, the mixture was stirred and heated to 170-190°C at atmospheric pressure. Distillation was performed at atmospheric pressure for 40 minutes, removing most of the MCB. Subsequently, a vacuum was applied to remove the remaining MCB and continuously remove phenol. For this purpose, the pressure was reduced to <1 mbar (approximately 0.6 mbar) over 90 minutes, and the bath temperature was gradually increased to 220°C. The mixture continued to condense at 220°C for 4 hours. The reaction was then stopped. M was obtained. w It is a yellow polymer with a concentration of 129,800 g / mol.

[0168] Example 44: In the presence of Kat1, CHDM (according to formula (1)) as the diol component reacts with HDI as the diisocyanate structural unit (comparative), and then reacts by adding Kat1 again with DPC as the carbonyl source, wherein the molar ratio is 2:1:1 (diol: diisocyanate: DPC). 63.23 g (438 mmol) CHDM, 0.006 g (163 ppm based on HDI) Kat1, and 100 g MCB were pre-loaded into a flask equipped with a reflux condenser and a dropping funnel. Under nitrogen protection, the mixture was stirred and heated to 120 °C at atmospheric pressure. Over 75 minutes, 36.76 g (219 mmol) HDI was added dropwise through the dropping funnel. The mixture was then stirred at 120 °C for 6 hours. The reaction was stopped and allowed to stand in the flask for six nights. Polycondensation was then carried out after six days. For this purpose, the dropping funnel and reflux condenser were removed, and a Wiegler column with a distillation bridge was installed. 47.03 g (220 mmol) DPC and 0.005 g (136 ppm based on HDI) Kat1 were added to the mixture. Under nitrogen protection, the mixture was stirred and heated to 170 °C to 200 °C at atmospheric pressure. Distillation at atmospheric pressure for 70 minutes removed most of the MCB. Subsequently, a vacuum was applied to remove the remaining MCB and continuously remove phenol. For this purpose, the pressure was reduced to <1 mbar (approximately 0.4 mbar) over 50 minutes, and the bath temperature was gradually increased to 220°C. The mixture continued to condense at 220°C for 15 minutes. The reaction was then stopped. A yellow polymer was obtained, but its solubility was too low to determine its molecular weight (M). w .

[0169] Example 45: TCD-DM (according to formula (2)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit, and then reacts with DPC as the carbonyl source in the presence of Kat1, wherein the molar ratio is 3:2:1.05 (diol: diisocyanate: DPC). 56.12 g (286 mmol) of TCD-DM and 50 g (191 mmol) of H12-MDI were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. The mixture was melted under nitrogen protection and heated to 130 °C with stirring at atmospheric pressure, then stirred at 130 °C for 2 hours. After 2 hours, 21.43 g (100 mmol) of DPC and 0.003 g (24 ppm based on the feedstocks TCD-DM, H12-MDI, and DPC) of Kat1 were added under countercurrent nitrogen. The mixture was heated to 180 °C and stirred for 20 minutes. 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 at 180 °C for 40 minutes, at 190 °C for 20 minutes, at 220 °C for 20 minutes, and at 240 °C for 20 minutes. The pressure was then reduced to <1 mbar (approximately 0.3 mbar) over 30 minutes, and the mixture was allowed to condense for another hour. The reaction was then stopped. M was obtained. wIt is a pale yellow polymer with a concentration of 51000 g / mol.

[0170] Example 46: TCD-DM (according to formula (2)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit, and then reacts with DPC as the carbonyl source in the presence of Kat1, wherein the molar ratio is 2:1:1 (diol: diisocyanate: DPC). 74.86 g (381 mmol) TCD-DM and 50 g (191 mmol) H12-MDI were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. The mixture was melted under nitrogen protection and heated to 130 °C with stirring at atmospheric pressure, then stirred at 130 °C for 2 hours. After 2 hours, 40.93 g (191 mmol) DPC and 0.005 g (30 ppm based on the raw materials TCD-DM, H12-MDI, and DPC) Kat1 were added under countercurrent nitrogen. The mixture was heated to 180 °C and stirred for 40 minutes. 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 at 180 °C for 30 minutes, at 190 °C for 30 minutes, at 200 °C for 10 minutes, at 210 °C for 10 minutes, and at 220 °C for 10 minutes. The pressure was then reduced to <1 mbar (approximately 0.3 mbar) over 15 minutes, and the mixture was allowed to continue condensing for 4 hours. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 76,000 g / mol.

[0171] Example 47: TCD-DM (according to formula (2)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit, and then reacts with DPC as the carbonyl source in the presence of Kat1, wherein the molar ratio is 3:1:2 (diol: diisocyanate: DPC). 56.12 g (286 mmol) TCD-DM and 25 g (95.3 mmol) H12-MDI were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. The mixture was melted under nitrogen protection and heated to 130 °C with stirring at atmospheric pressure, then stirred at 130 °C for 2 hours. After 2 hours, 40.83 g (191 mmol) DPC and 0.005 g (41 ppm based on the feedstocks TCD-DM, H12-MDI, and DPC) Kat1 were added under countercurrent nitrogen. The mixture was heated to 180 °C and stirred for 20 minutes. 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 at 180 °C for 30 minutes, at 190 °C for 30 minutes, at 200 °C for 10 minutes, at 210 °C for 10 minutes, and at 220 °C for 10 minutes. The pressure was then reduced to <1 mbar (approximately 0.3 mbar) over 15 minutes, and the mixture was allowed to continue condensing for 4 hours. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 75,600 g / mol.

[0172] Example 48: TCD-DM (according to formula (2)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit, and then reacts with DPC as the carbonyl source in the presence of Kat1, wherein the molar ratio is 4:1:3 (diol: diisocyanate: DPC). 59.83 g (305 mmol) of TCD-DM and 20 g (76.2 mmol) of H12-MDI were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. The mixture was melted under nitrogen protection and heated to 130 °C with stirring at atmospheric pressure, then stirred at 130 °C for 2 hours. After 2 hours, 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 Kat1 were added under countercurrent nitrogen. The mixture was heated to 180 °C and stirred for 20 minutes. 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 at 180 °C for 60 minutes, then at 220 °C for 10 minutes. Afterward, the pressure was reduced to <1 mbar (approximately 0.6 mbar) over 15 minutes, and the mixture was allowed to condense for another 4 hours. The reaction was then stopped. Get M w It is a pale yellow polymer with a concentration of 31900 g / mol.

[0173] Example 49:TCD-DM (according to formula (2)) as the diol component reacts with H12-MDI (according to formula (3)) as the diisocyanate structural unit, and then reacts with DPC as the carbonyl source in the presence of Kat1, wherein the molar ratio is 10:1:9 (diol: diisocyanate: DPC). 74.82 g (381 mmol) TCD-DM and 10 g (38.1 mmol) H12-MDI were pre-loaded into a flask equipped with a Wiegler column and a distillation bridge. The mixture was melted under nitrogen protection and heated to 130 °C with stirring at atmospheric pressure, then stirred at 130 °C for 2 hours. After 2 hours, 73.49 g (343 mmol) DPC and 0.009 g (57 ppm based on the feedstocks TCD-DM, H12-MDI, and DPC) Kat1 were added under countercurrent nitrogen. The mixture was heated to 180 °C and stirred for 20 minutes. Subsequently, a vacuum was applied to continuously remove phenol. For this purpose, the pressure was reduced to 100 mbar over 5 minutes. The mixture was stirred at 180 °C for 60 minutes, at 200 °C for 10 minutes, and then at 220 °C for 10 minutes. Then, the pressure was reduced to <1 mbar (approximately 0.6 mbar) over 10 minutes, and the mixture was allowed to continue condensing for 3 hours. The reaction was then stopped. M was obtained. w It is a pale yellow polymer with a concentration of 34,500 g / mol.

[0174] Table 4: Comparison of results from Examples 38 to 49 Example 1* Diol: Diisocyanate (molar ratio) <![CDATA[M w (g / mol)]]> Tg(°C) Carbonate: Carbamate impression** 38 E CHDM:H12-MDI (2:1) 61000 108 34:66 ductility 39 E CHDM:H12-MDI (2:1) 68800 110 34:66 ductility 40 E CHDM:H12-MDI (2:1) 114700 112 32:68 ductility 41 V ISB:H12-MDI (2:1) 16600 171 Undetermined brittleness 42 V HD:H12-MDI (2:1) 80900 52 Undetermined ductility 43 V CHDM:IPDI (2:1) 129800 110 Undetermined brittleness 44 V CHDM:HDI (2:1) Insoluble 49 Undetermined brittleness 45 E TCD-DM:H12-MDI (3:2) 51000 129 22:78 ductility 46 E TCD-DM:H12-MDI (2:1) 76000 121 34:66 ductility 47 E TCD-DM:H12-MDI (3:1) 75600 111 52:48 ductility 48 V TCD-DM:H12-MDI (4:1) 31900 99 64:36 brittleness 49 V TCD-DM:H12-MDI (10:1) 34500 85 88:12 brittleness * E represents the present invention, V represents the comparative example. A preliminary impression can be obtained by manually bending a solidified melt. If it does not break when bent, the material is described as "ductile"; otherwise, it is described as "brittle".

Claims

1. A thermoplastic poly(urethane-co-carbonate) comprising structures of formulas (I) and (II), wherein (I) Where each R in equation (I) 1 Each of the components is an aliphatic group having 6 to 18 carbon atoms, comprising at least one ring, and the ring may optionally contain at least one heteroatom. and (II) Where each R in equation (II) 2 Each is independently a bridged aliphatic structure having 6 to 18 carbon atoms, wherein the bridged structure comprises at least one ring, and the ring may optionally comprise at least one heteroatom, and wherein the connection between the bridged structure and the nitrogen atom shown in structure (II) is made by secondary or tertiary carbon atoms respectively. In formulas (I) and (II), the wavy lines respectively represent the connection of structures of formulas (I) and (II) in the poly(urethane-co-carbonate) chain, and at least some of the structures of formulas (I) and (II) are directly connected to each other to form urethane groups, and at least some other structures (I) are directly connected to each other with at least one other structure of formula (I) to form carbonate groups. Its features are, Thermoplastic poly(urethane-co-carbonate) contains less than 58 mol% to greater than 0 mol%, preferably less than 58 mol% to greater than 15 mol% of carbonate groups, based on the sum of carbonate and urethane groups in the poly(urethane-co-carbonate), wherein the molar percentage of carbonate and urethane groups is determined by... 13 The C-NMR spectrometry method was used to determine the weight-average molar mass of the thermoplastic poly(urethane-co-carbonate) from 40,000 g / mol to 200,000 g / mol.

2. The thermoplastic poly(urethane-co-carbonate) as described in claim 1, characterized in that, It does not contain ether groups and / or ester groups.

3. The thermoplastic poly(urethane-co-carbonate) as described in claim 1 or 2, characterized in that, The thermoplastic poly(urethane-co-carbonate) contains up to 60 mol% of aromatic groups, wherein these quantities are based on the total amount of aliphatic and aromatic groups.

4. The thermoplastic poly(urethane-co-carbonate) according to any one of claims 1 to 3, comprising structural formula (III) (III) Each R 1 The definition is shown in equation (I), where -CH2-R within parentheses 1 -CH2- groups can sometimes be R groups independently of each other. 6 However, this is contingent on at least some structures being -CH2-R. 1 -CH2- and R 6 It is an aliphatic alkylene group having 4 to 20 carbon atoms, which may be straight-chain, branched, or may contain at least one ring, wherein the at least one ring may contain at least one heteroatom, and wherein when R 6 When it contains at least one ring, R 6 At least on one side, preferably on both sides, the CH2- group is not incorporated into structure (III). And each R 2 The definition is shown in equation (II), and R is expressed as follows. 2 / R 7 Represents group R 2 At least sometimes they can be R independently of each other. 7 However, this is on the premise that at least some groups are R. 2 And R 7 yes - Straight-chain alkylene compounds containing 4 to 12 carbon atoms, - A cyclic aliphatic group containing 5 to 20 carbon atoms, wherein the structure R 7 The connection with at least one nitrogen atom shown in structure (III) is made via a primary carbon atom, or - Aromatic groups having 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. The wavy line represents the connection of the structure of formula (III) in the poly(urethane-co-carbonate) chain.

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

6. The thermoplastic poly(urethane-co-carbonate) according to any one of claims 1 to 5, characterized in that, R in equation (I) or equation (III) 1 Expressed by equation (1) or equation (2), (1)、 (2) In formulas (1) and (2), the positions marked with an asterisk "*" are the positions of the CH2- groups shown in formula (I) or formula (III).

7. The thermoplastic poly(urethane-co-carbonate) according to any one of claims 1 to 6, characterized in that, Structure R in formula (II) or formula (III) 2 Represented by one of equations (3) to (8), (3)、 (4)、 (5)、 (6)、 (7)、 (8)， In equations (3) to (8), the positions marked with an asterisk "*" indicate the positions of the nitrogen atoms shown in equation (II) or equation (III); In equation (3), each R 3 Each is independently either methyl or ethyl, p is 0, 1, or 2, and q is 0 or 1. In equation (5), each R 3 They are methyl or ethyl, and p is 0, 1 or 2.

8. A molding compound comprising the thermoplastic poly(urethane-co-carbonate) as described in any one of claims 1 to 7.

9. A molded article comprising the thermoplastic poly(urethane-co-carbonate) as described in any one of claims 1 to 7.

10. A method for producing the thermoplastic poly(urethane-co-carbonate) as described in any one of claims 1 to 7, comprising the following method steps: (i) Making at least one aliphatic diol of formula (Ia) Where each R in equation (Ia) 1 Each of the components is an aliphatic group having 6 to 18 carbon atoms, comprising at least one ring, and the ring may optionally contain at least one heteroatom. Reaction with at least one aliphatic diisocyanate of formula (IIa) Where R in equation (IIa) 2 It is a bridged aliphatic structure having 6 to 18 carbon atoms, wherein the bridged structure comprises at least one ring and the ring may optionally comprise at least one heteroatom, and wherein the connection between the bridged structure and the nitrogen atom shown in structure (IIa) is made by secondary or tertiary carbon atoms respectively. To form prepolymers, and (ii) Reacting the prepolymer obtained in step (i) with diaryl carbonate in the presence of at least one catalyst to obtain poly(urethane-co-carbonate). Its features are, In method step (i), the molar ratio of all used diols to all used diisocyanates is from 3.7:1 to 1.3:

1.

11. The method as described in claim 10, characterized in that, Between steps (i) and (ii), at least a portion of the unreacted aliphatic diol of formula (Ia) is removed from the prepolymer.

12. The method as described in any one of claims 10 or 11, characterized in that, At least one catalyst present in step (ii) of the method is an ammonium salt, a phosphonium salt, or an organic base.

13. The method according to any one of claims 10 to 12, characterized in that, R in equation (Ia) 1 Expressed by equation (1) or equation (2), (1)、 (2)， In formulas (1) and (2), the positions marked with an asterisk "*" are the positions of the CH2- groups shown in formula (Ia).

14. The method according to any one of claims 10 to 13, characterized in that, Structure R in equation (IIa) 2 Represented by one of equations (3) to (8), (3)、 (4)、 (5)、 (6)、 (7)、 (8)， In equations (3) to (8), the positions marked with an asterisk "*" represent the positions of the nitrogen atoms as shown in equation (IIa), and In equation (3), each R 3 Each is independently methyl or ethyl, p is 0, 1, or 2, q is 0 or 1, and In equation (5), each R 3 They are methyl or ethyl, and p is 0, 1 or 2.

15. The method as described in claim 14, characterized in that, R in equation (IIa) 2 The structure is represented by equation (3), where p = 0 and q = 1.

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