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

Abstract

The present invention relates to a process for the production of thermoplastic poly(urethane-co-carbonate) by a high viscosity urethane diol prepolymer. The transparent thermoplastic poly(urethane-co-carbonate) has a high glass transition temperature of > 110°C and M w a molar mass equal to at least 40000 g / mol to preferably 190000 g / mol and a ductile behavior at room temperature. The polymer can be processed in common plasticizing processes to form molded parts.

Description

[0001] This invention relates to an improved method for producing thermoplastic poly(urethane-co-carbonate) from high-viscosity urethane diol prepolymers, and to the urethane diol prepolymers themselves, and the thermoplastic poly(urethane-co-carbonate) produced therefrom.

[0002] Aromatic polycarbonates are renowned for their excellent mechanical, optical, heat distortion, and weather resistance properties. However, due to the presence of aromatic groups, there are other properties requiring improvement, such as light transmittance, birefringence, and yellowing tendency. Furthermore, depending on the production method, a large amount of phenol is generated as condensate, which requires complex industrial collection and processing. Aliphatic polycarbonates show improvements in the aforementioned areas requiring further refinement, as well as in chemical resistance, but they typically have a low glass transition temperature, resulting in poor heat distortion resistance. Therefore, efforts are being made to develop polymers that combine the excellent properties of both aromatic and aliphatic polycarbonates while minimizing their negative properties and generating as little phenol as possible during production.

[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 blends, but due to their aromatic groups, they also introduce the aforementioned disadvantages (especially yellowing tendency, poor light 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 polymer with a glass transition temperature of at least 110°C. This polymer should also possess good optical properties (especially transparency). The polymer preferably also has high heat deformability. The polymer should preferably be processed using plasticizing methods commonly used for aromatic polycarbonates, such as injection molding, (co)extrusion, blow molding, and deep drawing. For this purpose, it is particularly advantageous that the thermoplastic polymer is amorphous. The thermoplastic polymer should also preferably possess good mechanical properties, for example, properties comparable to those of aromatic polycarbonates. The thermoplastic polymer is particularly preferably at least ductile fracture at room temperature. Compared to aromatic polycarbonates, the production of this thermoplastic polymer should preferably produce less phenol.

[0007] The applicant has already proposed the subject matter of European Patent Application No. 23217149.6, which has not yet been published, as a solution to the above objectives. The poly(urethane-co-carbonate) and its preparation method described in that patent application have achieved at least one of the above objectives, preferably all of them.

[0008] The applicant has now unexpectedly discovered that the polymer production method can be further optimized if the excess ratio of diol to diisocyanate is lower, particularly if the molar ratio of all diols used to all diisocyanates used is 1.30:1.0 to 1.01:1.0, especially preferably 1.27:1.0 to 1.05:1.0, and particularly preferably 1.25:1.0 to 1.10:1.0.

[0009] This allows for the production of high-viscosity prepolymers. Another advantage is that, due to the high molecular weight and the resulting low proportion of terminal OH groups, less distillate is generated as phenol during the polycondensation reaction. Preferably, the distillate as phenol is less than 15% by weight, based on all starting materials (excluding catalyst).

[0010] The subject of this invention is therefore a method for producing thermoplastic poly(urethane-co-carbonate), comprising the following method steps: (i) Making at least one aliphatic diol of formula (Ia) (Ia) Where each R in equation (Ia) 1 Each of the components is an aliphatic group having 4 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) (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 through 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 from 1.30:1.0 to 1.01:1.0, particularly preferably from 1.27:1.0 to 1.05:1.0, and more preferably from 1.25:1.0 to 1.10:1.0.

[0011] The subject of this invention is still thermoplastic poly(urethane-co-carbonate), which includes the structures of formulas (I) and (II). (I) Where each R in equation (I) 1 Each of the above is an aliphatic group having 4 to 18 carbon atoms, comprising at least one ring, and the ring may optionally comprise at least one heteroatom; and (II) Where each R in equation (II) 2Each 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 connections 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 the fact that the thermoplastic poly(urethane-co-carbonate) contains ≥1 mol% to ≤15 mol% 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 The thermoplastic poly(urethane-co-carbonate) was determined by C-NMR spectroscopy, and its weight-average molar mass was at least 40,000 g / mol. The thermoplastic poly(urethane-co-carbonate) is preferably prepared according to the method of the present invention.

[0012] According to the present invention, "poly(urethane-co-carbonate)" is used to describe polymers having the characteristics of the present invention.

[0013] R 1 Defined as "an aliphatic group having 4 to 18 carbon atoms, comprising at least one ring and optionally comprising at least one heteroatom". Therefore, R 1 This encompasses both "cyclic aliphatic groups" and "heterocyclic aliphatic groups." For the purposes of this invention, "cyclic aliphatic" preferably means that the group consists only of carbon and hydrogen atoms. Here and elsewhere, "cyclic aliphatic" according to this invention is preferably understood as a group that is a cycloalkylene group. "Cycloalkylene" preferably refers to a bridging cycloalkane structure that has two hydrogen atoms removed from different carbon atoms. This applies as long as the defined total number of carbon atoms is present and R... 1 If the overall structure contains at least one ring, then a connection via a straight-chain alkylene group to the oxygen atom shown in formula (I) is not excluded. The two carbon atoms from which two hydrogen atoms are removed can be arbitrary, i.e., any portion of the ring or straight-chain alkylene group (if present). Furthermore, according to the invention, the cycloalkylene group can also be connected to or fused with at least one other cyclic aliphatic ring via a bridging structure. The cyclic aliphatic group can also have one or more double bonds. Here and in all other places describing the polymer, method, and prepolymer, the aliphatic group R... 1 The number of carbon atoms in it is preferably 6 to 18, more preferably 6 to 10.

[0014] According to the present invention, "heterocyclic aliphatic" preferably refers to, in contrast to "cyclic aliphatic", at least one ring of each group is formed not only by connected carbon atoms, but also by at least one carbon atom in the ring being replaced by a heteroatom, preferably nitrogen, oxygen, sulfur or phosphorus, wherein the heterocyclic aliphatic group preferably contains oxygen or nitrogen, and oxygen is particularly preferred as a heteroatom.

[0015] 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.

[0016] It will be obvious to those skilled in the art that when R in the diol of formula (Ia) 1 R in diisocyanates of formula (IIa) 2 When more than one ring is involved, one or more carbon atoms from the 4 to 18 or 6 to 18 carbon atoms described in the claims may also be part of two or more rings simultaneously.

[0017] The molar ratio of all the diols used, especially the (cyclic) aliphatic diols of formula (Ia), to all the diisocyanates used, especially the (cyclic) aliphatic diisocyanates of formula (IIa), can particularly affect the resulting ratio of carbonate groups to urethane groups in poly(urethane-co-carbonate).

[0018] 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 diols. This can be one or more aliphatic diols of formula (Ia). It is particularly evident that when R... 1 When more than one ring is involved, one or more of the 4 to 18 carbon atoms may also be part of two rings. R in formula (Ia) 1 Each of the groups is an aliphatic group, comprising 4 to 18 carbon atoms and containing at least one ring, which may optionally contain at least one heteroatom, preferably an oxygen atom.

[0019] Very particularly preferred, 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).

[0020] In addition to the aliphatic diol shown in 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%, also preferably at most 40 mol%, particularly preferably at most 25 mol%, also preferably at most 10 mol%, and most especially preferably at most 45 mol%, based on all diols used. Most preferably, no other diols are used except for at least one aliphatic diol of formula (Ia).

[0021] The 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 alkylene group is an aliphatic alkylene group having 4 to 20, preferably 5 to 18, more preferably 6 to 16 carbon atoms. This 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 when R... 6 When at least one ring is included, at least one OH group is not a primary alcohol group. "At least one OH group is not a primary alcohol group" means that at least one OH group is not incorporated into formula (X) via a CH2- group, but belongs to a secondary or tertiary alcohol functional group. Preferably, neither of the two OH groups is incorporated into formula (X) via a CH2- group. Clearly, "incorporated via" means that the corresponding incorporated group is part of formula (X).

[0022] However, preferably, diols containing ether groups are not used in method step (i) of the method of the present invention. Also preferably, diols containing ester groups are not used in method step (i) of the method of the present invention. In particular, polyether polyols and / or polyester polyols are not used in method step (i) of the method of the present invention. Those skilled in the art can also deduce other particularly preferred diols based on the preferred embodiments of formula (Ii) described below.

[0023] In this context, it will be apparent that the invention frequently refers to "at least one" compound, such as a diol or diisocyanate, and "other" compounds. The presence of the compound referred to herein as "at least one" is mandatory, while (one or more) other compounds may be present additionally. Therefore, those skilled in the art will also be able to determine the ratio of diol to diisocyanate.

[0024] In method step (i), at least one aliphatic diisocyanate of formula (IIa) is also used. Clearly, the aliphatic diisocyanate of formula (IIa) can be used as the sole diisocyanate. R in formula (IIa) 2 Preferred to be R in equation (II) above 2 The definition is the same. R 2 In particular, C6 to C that meet the above preferred definition 18 Cycloalkylene, wherein taking into account the effect of R 2 The aforementioned limitations. A particularly preferred feature of the method of the present invention is 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 shown in equation (IIa); 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.

[0025] In step (i) of the method of the present invention, at least one aliphatic diol of formula (Ia) is particularly preferred, wherein R 1 Having the structure of formula (1) and / or (2), and formula (IIa), where R 2The structure is represented by equation (3), where p = 0 and q = 1. Particularly preferred is that the structure of equation (3) (where p = 0 and q = 1) can be a mixture of different structures. A mixture of 4,4'- and 2,4'-, and optionally 2,2'- isomers, is preferred here. Furthermore, a mixture of at least 80 mol% of the structure being the 4,4'- isomer and the remainder being the 2,4'- or 2,2'- isomer is preferred.

[0026] In addition to the aliphatic diisocyanate shown in 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 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%, based on all diisocyanates used. "At most" indicates that the respective limits are included within the range. Most preferably, no other diisocyanates are used except for at least one aliphatic diisocyanate of formula (IIa).

[0027] The one or more diisocyanates in method step (i) are preferably at least one diisocyanate of formula (Xi). OCN-R 7 -NCO (Xi), Where each R in equation (Xi) 7 yes - Straight-chain alkylene compounds containing 4 to 12 carbon atoms, - Contains 5 to 20, preferably 7 to 18, cyclic aliphatic groups, wherein the structure R 7 The connection with at least one nitrogen atom shown in structure (Xi) is made via a primary carbon atom, or - Aromatic groups containing 6 to 18 carbon atoms.

[0028] Those skilled in the art can also deduce other particularly preferred diisocyanates based on the preferred embodiments of formula (IIi) mentioned later.

[0029] Very particularly preferred, except for R having conformity to formula (1) and / or (2) 1 diols and R having at least one of formulas (3) to (8), especially formula (3). 2 Apart from diisocyanates, no other diols and / or diisocyanates are used.

[0030] In step (i) of the method of the present invention, a prepolymer is prepared. The subject matter of the present invention is still preferably the prepolymer prepared by step (i).

[0031] According to the present invention, a prepolymer is understood to refer to a polymer precursor. The urethane diol prepolymer is composed of diol and diisocyanate structural units. It is a reactive oligomer. In the prepolymer of the present invention, the terminal OH group is a reactive functional group.

[0032] OH-terminated prepolymers preferably include those with structural formula (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 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 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 - An aromatic group containing 6 to 18 carbon atoms, and m is the arithmetic mean of the repeating units, and is ≥4, preferably ≥4.5, particularly preferably ≥4.75, and very particularly preferably ≥5.0. The arithmetic mean m of the repeating units is preferably ≤25.0, particularly preferably ≤21.0, and very particularly preferably ≤10.0.

[0033] The prepolymer is more preferably an OH-terminated urethane prepolymer having a structure factor as defined below, having the structure of formula (IIIa). Where each R in equation (IIIa)1 Each of the components is an aliphatic group having 4 to 18 carbon atoms, comprising at least one ring, and the ring may optionally contain at least one heteroatom. and Where each R in equation (IIIa) 2 Each is an independent bridging aliphatic structure having 6 to 18 carbon atoms, wherein the aliphatic structure comprises at least one ring, and wherein the ring may optionally comprise at least one heteroatom, and wherein the connection between the bridging structure and the nitrogen atom shown in structure (IIIa) is made via secondary or tertiary carbon atoms. Where m is the arithmetic mean of the repeating units, and is ≥ 4.0, preferably ≥ 4.5, particularly preferably ≥ 4.75, and very particularly preferably ≥ 5.0. The arithmetic mean m of the repeating units is preferably ≤ 25.0, more preferably ≤ 21.0, and very particularly preferably ≤ 10.0.

[0034] It is preferred to use only diols of formula (Ia) and diisocyanates of formula (IIa).

[0035] The urethane prepolymer contains urethane groups -NH-CO-O-. The structure factor, referred to as "m" in formulas (III) and (IIIa), represents the number of diisocyanate structural units that make up the prepolymer. It is the arithmetic mean of the repeating units in square brackets. The structure factor has an upper limit because it is only a "prepolymer," i.e., a reactive structural unit with terminal OH groups as reactive functional groups.

[0036] Those skilled in the art can determine the arithmetic mean m of the repeating units using known methods. In particular, m can be determined by gel permeation chromatography, preferably using the gel permeation chromatography described below. In this method, different peaks can be 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.

[0037] The OH-terminated urethane prepolymer particularly preferred according to the present invention is R1 represented by formula (1) or (2) and R 2 Prepolymers represented by one of equations (3) to (8): (1) (2), In formulas (1) and (2), the positions marked with an asterisk "*" represent the positions of the CH2- groups shown in formula (III) or (IIIa). (3) (4) (5) (6) (7) (8), Especially (3), In equations (3) to (8), the positions marked with an asterisk "*" represent the positions of the nitrogen atoms shown in equation (III) or (IIIa); 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.

[0038] "OH-terminated" refers to the presence of OH groups at both ends of the urethane prepolymer. Therefore, the prepolymer can also be called "urethane diol". Those skilled in the art can determine the amount of reactive OH groups using known methods. The concentration of OH groups can be determined, in particular, by titration as a hydroxyl value (also called OH value) in mg KOH / g. The OH value of the urethane prepolymer is preferably 14 to 85 mg KOH / g, more preferably 16 to 80 mg KOH / g, particularly preferably 18 to 75 mg KOH / g, and very particularly preferably 20 to 70 mg KOH / g, wherein each OH value is preferably determined by titration based on DIN EN ISO 4629-2, where "based on" means using pyridine instead of N-methyl-2-pyrrolidone as the base. This method is defined as method number 2011-0232602-92D in Currenta GmbH & Co. OHG, which is available upon request from the company.

[0039] The number-average molecular weight M of the prepolymer n Preferably, the molecular weight is from 1500 g / mol to 10000 g / mol, more preferably from 1750 g / mol to 9000 g / mol, particularly preferably from 2000 to 7500 g / mol, and very particularly preferably from 2250 to 7000 g / mol. This number-average molecular weight M n Preferably, the molecular weight is determined by gel permeation chromatography. Unless otherwise specified, the number-average molecular weight (M) of the present invention is... n ) and / or all other weight-average molecular weights (M wThe determination is particularly preferred by gel permeation chromatography (GPC), with degassed tetrahydrofuran (THF) as the mobile phase, polystyrene as the standard (preferably based on DIN EN ISO 13885-1:2021-11) and calibrated using polystyrene. The GPC analytical unit includes a pump (e.g., Agilent 1200 Infinity II IsoPump), an injector (e.g., Agilent 1100 Infinity II ALS), a column oven (e.g., Shimadzu CTO-10A), and preferably one or more standard commercial GPC columns (e.g., PSS SDV 5 µm, PSS SDV 1000 Å, PSS SDV 100 Å, PSS SDV 50 Å) in series for size exclusion chromatography, chosen to adequately distinguish the molar mass of the prepolymer and polymer. Detection is preferably performed using refractive index (e.g., via Agilent 1260 Infinity II RID). Calibration was performed using narrow-distribution polystyrene standards (for prepolymers, e.g., ReadyCal Kit Polystyrene low, part number: PSS-PSKITR1L, nominal molecular weight 266-66000 Da; or for polymers, e.g., ReadyCal Kit Polystyrene, part number: PSS-PSKITR1, nominal molecular weight 474-2520000 Da). Molar mass averages outside this range were calculated by extrapolation. For sample preparation, 20-40 mg of sample was dissolved in 5-10 ml of THF with gentle shaking for 2 hours, followed by filtration through a 0.45 µm PTFE filter. 40 µL of the solution was injected into the GPC analytical unit, and determination was performed using degassed THF as the mobile phase at a flow rate of 0.6 ml / min and a temperature of 30 °C. The general method is defined in Currenta GmbH & Co. OHG AM 2011-0623701-09D, available upon request from Currenta.

[0040] The glass transition temperature T of the prepolymer of this invention g Preferably, the glass transition temperature is ≥80°C, more preferably ≥80°C to ≤145°C, even more preferably ≥85°C to ≤140°C, particularly preferably ≥90°C to ≤135°C, and very particularly preferably ≥95°C to ≤130°C. The glass transition temperature is determined by dynamic differential scanning calorimetry, preferably according to DIN EN ISO 11357-1:2022-02 and DIN EN ISO 11357-2:2020-08 standards at a heating rate of 20 K / min.

[0041] In step (i), at least one diol of formula (Ia) may be added beforehand. In this case, the diisocyanate of formula (IIa) is then added entirely or over a longer period of time. However, the diol of formula (Ia) and the diisocyanate of formula (IIa) may also be added to the reactor simultaneously. Step (i) is preferably carried out at a heating medium temperature in the range of 110°C to 265°C, more preferably 140°C to 260°C, particularly preferably 170°C to 255°C, and very particularly preferably 200°C to 250°C. Since the reaction is exothermic, it is also preferably carried out using a reverse cooling method.

[0042] Method step (i) can be performed under a nitrogen atmosphere at standard pressure. However, this method step can also be performed under reduced pressure or high pressure.

[0043] Method step (i) is preferably performed for such a long time that all present diisocyanates have essentially reacted. This can be verified, for example, by measuring the NCO content.

[0044] 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. When a catalyst is used in method step (i), carbamate catalysts known to those skilled in the art can be used. 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, particularly (3-dimethylaminopropylamine)urea), and tin catalysts (e.g., monoalkyltin oxide, dialkyltin oxide, dialkyltin dilaurate, tin octanoate).

[0045] The catalyst used may preferably be (A) urea, urea derivatives, and / or (B) the aforementioned amines and amino ethers, characterized in that the amines and amino ethers contain a functional group that reacts chemically with isocyanates. This functional group is preferably hydroxyl, primary, or secondary amino. These particularly preferred catalysts have the advantage of significantly reduced 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-methylpropane-1,3-diamine, and 3-dimethylaminopropylamine and their derivatives, and similar molecules, wherein the dimethylamino group is substituted with a pyrrolidinyl group according to WO 2022 / 112157 A1.

[0046] In method step (i), monobutyltin oxide and / or dibutyltin oxide are particularly preferred as catalysts.

[0047] When a catalyst is used in step (i) of the method, it is preferred to use an amount of 1 ppm to 1000 ppm, particularly preferred to use 30 ppm to 500 ppm, and very particularly preferred to use 50 ppm to 170 ppm, based on the mass of all diisocyanates used.

[0048] In this invention, unless otherwise stated, ppb and ppm should be understood as parts by weight.

[0049] The prepolymer obtained by method step (i) is (substantially) OH-terminated by a specific ratio of diol to diisocyanate. Furthermore, unreacted aliphatic diol of formula (Ia) (and possibly diol of formula (X) if present) is typically present immediately after method step (i) because an excess of diol has been used. The one or more diols may be present in method step (ii) or removed prior to the step.

[0050] In one aspect of the method of the present invention, it 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, the at least one other aliphatic diol, preferably of formula (X), may also be removed herein.

[0051] Preferably, unreacted aliphatic diols of formula (Ia) (and optionally aliphatic diols of formula (X) and other optional aliphatic diols) are removed, for example, by distillation, precipitation, and / or a thin-film evaporator. Those skilled in the art are familiar with various methods that can be used to remove aliphatic diols of formula (Ia).

[0052] 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 a portion of 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).

[0053] The molar ratio of the diaryl carbonate used, based on the presence of OH groups, is preferably from 1.2:1 to 0.95:1, more preferably from 1.11:1 to 0.98:1, and very particularly preferably from 1.07:1 to 0.99:1 (the first number represents the diaryl carbonate, and the second number represents the presence of OH groups). This may be derived from the prepolymer of step (i) or optionally from unreacted diols and / or other diols. The concentration of OH groups in the prepolymer is preferably determined by measuring the OH value as described above. However, it can also be determined by theoretical calculations.

[0054] According to the invention, method steps (i) and (ii) may not be completely separable from each other. Therefore, the diaryl carbonate in method step (ii) and the catalyst used in method step (ii) may already be present in method step (i). In this case, it is impossible to completely avoid the anticipated reaction in method step (ii) occurring in small amounts in step (i). However, this can be minimized (e.g., by temperature control). According to the invention, it is anticipated that the reaction of the OH group with the NCO group occurs first (method step (i)), followed by the reaction of the OH group with the diaryl carbonate (method step (ii)). Those skilled in the art can perform these anticipated reactions such that they occur primarily in the stated order.

[0055] Preferably, the prepolymer obtained in step (i) is not separated. This means that step (ii) is preferably performed immediately after step (i). This can be achieved, for example, by increasing the temperature and applying a vacuum, when at least a portion of the diaryl carbonate and catalyst are already present in step (i). This can also be achieved by adding the diaryl carbonate and / or catalyst and increasing the temperature and applying a vacuum.

[0056] Step (ii) is preferably performed at a heating medium temperature of 210°C to 270°C, more preferably 220°C to 265°C, and very particularly preferably 230°C to 260°C. The temperature shown here is preferably the final temperature. According to the invention, the final temperature can be reached by gradually increasing the temperature.

[0057] The reaction in step (ii) typically produces a condensation product. To shift the reaction equilibrium, it is advantageous to apply a vacuum in step (ii). The vacuum in step (ii) is preferably from 500 mbar to 0.01 mbar, more preferably from 200 mbar to 0.01 mbar. It is particularly preferred that the vacuum be gradually reduced. The vacuum in the final stage is very particularly preferably from 10 mbar to 0.01 mbar.

[0058] A preferred feature of the method of the present invention is that the 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.

[0059] The useful catalysts 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, and oxides of lithium, sodium, potassium, cesium, magnesium, calcium, barium, yttrium, titanium, manganese, iron, zinc, tin, and bismuth, as well as nitrogen and phosphorus bases, such as tetramethylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium fluoride, tetramethylammonium tetraphenylborate, tetraphenylphosphonium fluoride, tetraphenylphosphonium tetraphenylborate, dimethyl diphenylammonium hydroxide, tetraethylammonium hydroxide, hexadecyltrimethylammonium tetraphenylborate, hexadecyltrimethylammonium phenolate, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) ), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or guanidine systems, such as 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'-hexene di-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7,7'-decene di-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7,7'-dodecylene di-1,5,7-triazabicyclo[4.4.0]dec-5-ene, or phosphazenes, such as phosphazene base P1-t-Oct = tert-octyliminotris(dimethylamino)phosphine, phosphononitrile base P1-t-Butyl = tert-butyliminotris(dimethylamino)phosphine, BEMP = 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diaza-2-phosphine.

[0060] 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 15 Arylalkyl or C5 to C6 cycloalkyl, preferably phenyl.

[0061] 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.

[0062] The amount of these catalysts can be from 0.1 to 1000 ppm, preferably from 0.5 to 500 ppm, particularly preferably from 1 to 200 ppm, and very particularly preferably from 1 to 100 ppm, based on the total starting materials (one or more diols + one or more diisocyanates + diaryl carbonates).

[0063] The method of the present invention yields thermoplastic poly(urethane-co-carbonate) with excellent optical properties. This is particularly attributed to the amorphous nature of the thermoplastic poly(urethane-co-carbonate) of the present invention. In particular, the poly(urethane-co-carbonate) of the present invention is transparent. Preferably, in the present invention, the term "transparent" should be understood as the injection-molded plate having a transmittance of at least 20% in the VIS spectral region (380 to 780 nm, TVIS transmittance), preferably at least 50%, more preferably at least 70%, particularly preferably at least 80%, and very particularly preferably at least 88%, as measured according to DIN ISO 13468-2:2006 (D65, 10°, sample plate layer thickness: 4 mm). These injection-molded plates preferably also have a haze of less than 30%, more preferably less than 20%, more preferably less than 10%, more preferably less than 7%, and very particularly preferably less than 3%, as measured according to ASTM D1003:2013. This specifically refers to injection-molded plates with visual transparency, i.e., those depicting their background.

[0064] Similarly, due to its amorphous nature, the thermoplastic poly(urethane-co-carbonate) of the present invention is particularly suitable for known plasticizing methods of aromatic polycarbonates. The poly(urethane-co-carbonate) of the present invention offers the advantage of properties similar to conventional aromatic polycarbonates. Because the poly(urethane-co-carbonate) of the present invention is amorphous, it particularly does not have significant shrinkage, preferably less than 1% in each direction. Those skilled in the art are familiar with the term "shrinkage" in the field of polymers, particularly crystalline polymers. This term preferably 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.

[0065] The thermoplastic poly(urethane-co-carbonate) of the present invention also possesses good mechanical properties, such as ductile fracture at least at room temperature. Therefore, the thermoplastic poly(urethane-co-carbonate) of the present invention particularly exhibits properties comparable to, and preferably superior to, conventional aromatic polycarbonates (e.g., bisphenol A-based polycarbonates). Specifically, the thermoplastic poly(urethane-co-carbonate) of the present invention not only possesses good mechanical properties but also good chemical resistance (especially hydrolysis resistance), good transmittance, 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, particularly preferably equal to 0% by weight, thereby reducing, and especially avoiding, the common disadvantages associated with the presence of aromatic groups in the polymer.

[0066] Preferably, the thermoplastic poly(urethane-co-carbonate) of the present invention obtained by the method of the present invention can be processed into all types of molded articles. It can also be processed with other thermoplastic plastics and / or polymer additives into thermoplastic molding compounds, which are then molded into molded articles. Other subjects of the present invention are molded articles and molding compounds made from thermoplastic compositions comprising 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., heat stabilizers, hydrolysis and heat aging stabilizers, and transesterification inhibitors), flow promoters, compatibilizers, dyes and pigments, impact modifiers, and fillers and reinforcing agents.

[0067] Molded articles made from thermoplastic compositions comprising 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 from pre-prepared sheets or films by deep drawing.

[0068] According to the present invention, by using both cyclic aliphatic or heterocyclic aliphatic diols and cyclic or heterocyclic aliphatic diisocyanates, and by using a ratio of all used diols to all used diisocyanates of 1.30:1.0 to 1.01:1.0, more preferably 1.27:1.0 to 1.05:1.0, and very particularly preferably 1.25:1.0 to 1.10:1.0, a thermoplastic poly(urethane-co-carbonate) with a high glass transition temperature, preferably ≥110°C, more preferably ≥115°C, and especially preferably ≥120°C, is obtained. Furthermore, it is particularly advantageous that, after step (i), at least partially, the remaining (unreacted) aliphatic diols (formula (Ia) and optionally (X)) are removed. This affects the glass transition temperature and further increases it. Therefore, the value of the glass transition temperature can be selectively adjusted. However, this always depends on the chemical properties of the diols and diisocyanates used. Those skilled in the art will understand how this will affect the presence or absence of repeating units (V), particularly as shown below. For example, the thermoplastic poly(urethane-co-carbonate) of the present invention typically contains repeating units of formula (V) when unreacted diols are still present in the prepolymer at the start of method step (ii).

[0069] Surprisingly, it has been found that the glass transition temperature of the poly(urethane-co-carbonate) with the minimum molar mass, preferably prepared by the method of the present invention, comprising 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, is preferably at least 110°C, more preferably ≥115°C, and particularly preferably ≥120°C. Furthermore, relatively little phenol is generated during the production process. 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 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, and in particular, a glass transition temperature of at least 110°C can be selectively achieved.

[0070] Preferably, the glass transition temperature of the thermoplastic poly(urethane-co-carbonate) is at least 110°C, more preferably ≥110°C to ≤150°C, particularly preferably ≥115°C to ≤145°C, and very particularly preferably ≥120°C to ≤140°C. Glass transition temperature (T gThe determination is preferably performed by dynamic differential scanning calorimetry (DSC) according to standards DIN EN ISO 11357-1:2022-02 and DIN EN ISO 11357-2:2020-08. Specifically, a heating rate of 20 K / min is used under nitrogen atmosphere, and T... g The inflection point in the second heating process was identified. The thermoplastic poly(urethane-co-carbonate) of this invention exhibits correspondingly good heat deformation resistance. The glass transition temperature within a specific range allows the thermoplastic poly(urethane-co-carbonate) of this invention to be used in conventional plasticizing methods (e.g., injection molding, (co)extrusion, blow molding, deep drawing). The ratio of carbonate groups to urethane groups can be influenced, for example, by the ratio of one diol / multiple diols used to one diisocyanate / multiple diisocyanates used. Similarly, different copolymers with different carbonate group to urethane group ratios can be mixed in a blend to specifically adjust the ratio.

[0071] The proportion of carbonate groups in the thermoplastic poly(urethane-co-carbonate) is ≥1 mol% to ≤15 mol%, preferably ≥3 mol% to ≤14 mol%, more preferably ≥5 mol% to ≤13 mol%, based on the total number of carbonate and urethane groups in the poly(urethane-co-carbonate), wherein the molar percentage of carbonate and urethane groups is determined by... 13 C-NMR spectroscopy determination. Those skilled in the art can use this method to determine the proportions of carbonate groups and urethane groups. For example, the polymer can be dissolved in CDCl3. If an insoluble residue is present, 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 as ratios. This is a method known to those skilled in the art.

[0072] Surprisingly, it was discovered that polymers with a glass transition temperature of at least 110°C can be obtained by using a specific ratio of carbonate groups.

[0073] The weight-average molar mass of the thermoplastic poly(urethane-co-carbonate) is also 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 190,000 g / mol, more preferably from 45,000 g / mol to 160,000 g / mol, and very particularly preferably from 50,000 g / mol to 130,000 g / mol. The molar mass is preferably determined by the method described above. It has been found that the poly(urethane-co-carbonate) of the present invention has good properties, particularly good thermoplasticity, within this specific molar mass range. Similarly, mechanical properties, particularly toughness behavior at least at room temperature, are also good within this molar mass range. It has also been found that when aromatic groups are present in the poly(urethane-co-carbonate) of the present invention, a lower molar mass can optionally be present, and good mechanical properties, particularly ductility, can still be present.

[0074] The glass transition temperature and molar mass within the aforementioned range enable 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.

[0075] The thermoplastic poly(urethane-co-carbonate) of the present invention 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. Also preferably, and particularly preferably simultaneously, 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 preferred to use components that are as pure as possible. Furthermore, it is apparent that these impurities may be present even in closed formulations of the compounds used.

[0076] Preferably, the structure is not included when the structure of formula (II) is directly connected to the structure of formula (II). This will generate a urea group.

[0077] 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.

[0078] 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: .

[0079] 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) to each other at least one other structure of formula (I).

[0080] 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).

[0081] In the poly(urethane-co-carbonate) of the present invention, the structures of formula (IA) and (IIA) are preferably randomly distributed. This is especially applicable when other structures different from those of formula (I) and (II) / formula (IA) and (IIA) also exist.

[0082] The poly(urethane-co-carbonate) of the present invention is preferably prepared by the method of the present invention described in more detail above. In this method, a diol is first reacted with a diisocyanate. The resulting prepolymer is then reacted with a carbonyl 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 functional groups 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 functional groups 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.

[0083] 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). Those skilled in the art will understand how structures (I) and (II) are proportioned, particularly structures (IA) and (IIA) are included. Particularly preferably, at least 50%, preferably at least 75%, more preferably at least 80%, very particularly preferably at least 90%, and especially preferably at least 95% of the poly(urethane-co-carbonate) of the present invention is composed of the structures of formulas (I) and (II). Furthermore, those skilled in the art will understand how structures (I) and (II) are proportioned, particularly structures (IA) and (IIA) are included.

[0084] 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 independently an aliphatic group having 4 to 18 carbon atoms, comprising at least one ring, and the ring may optionally comprise at least one heteroatom, preferably an oxygen atom, and 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 multiple rings are involved, one or more of the 4 to 18 carbon atoms can also be part of two rings.

[0085] R in equations (I), (IA), (IIA) and (IV), (IVi), (V) and (VI) 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) and (IV), (IVi), (V) and (VI) shown later.

[0086] Very particularly preferably, formula (I) is represented by the following formula (I1) or (I2): (I1), (I2), In formulas (I1) and (I2), the wavy lines respectively represent the linkages of the structures of formulas (I1) and (I2) within the poly(urethane-co-carbonate) chain. Most preferably, formula (I1) is based on cyclohexane-1,4-diethanol.

[0087] 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 Each of the components independently 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 and 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 6At 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).

[0088] However, if the structure of formula (Ii) also exists, then at least one other structure of formulas (Iia) to (Iid) is particularly preferred. (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.

[0089] In the poly(urethane-co-carbonate) of the present invention, if other structures of formula (Ii) or particularly preferred structures (Iia) to (Iid) are included, the amount of such structures is preferably selected so that the glass transition temperature of the resulting poly(urethane-co-carbonate) is maintained above 110°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%, even more preferably at most 40 mol%, particularly preferably at most 25 mol%, even more 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). Most preferably, none are present, therefore 0 mol% of other structures of formula (Ii) are present. However, if at least one structure of formula (Ii) or preferred structures of formulas (Iia) to (Iid) exists, the term "at most" here means that more than 0 moles are present.

[0090] 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.

[0091] According to the present invention, poly(urethane-co-carbonate) further comprises the structure of formula (II). (II), Where each R in equation (II) 2 Each 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, 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.

[0092] 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.

[0093] Particularly preferred is the structure R in formula (II), (IIA), or formulas (IV), (IVi), (V), or (VI) 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), (IV), (IVi), (V), or (VI) shown later; 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.

[0094] Very particularly preferred, R 2 The 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.

[0095] 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, - Contains 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 - An aromatic group containing 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).

[0096] However, if the structure of formula (IIi) exists, the poly(urethane-co-carbonate) of the present invention not only includes the structure of formula (II), but preferably includes at least one other structure of formulas (IIia) to (IIih): (IIia), (IIib), (IIic) (IIid) (IIie) (IIif) (IIig) (IIih) in Each R in equation (IIib) 18 Each 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 equations (IIia) to (IIih), the positions marked with an asterisk "*" represent the positions of the nitrogen atoms shown in equation (IIi).

[0097] In the poly(urethane-co-carbonate) of the present invention, the amount of other structures or preferred structures (IIia) to (IIih) of formula (IIi) is preferably selected such that the glass transition temperature of the resulting poly(urethane-co-carbonate) is ≥110°C, more preferably ≥115°C, and particularly preferably ≥120°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 at most 75 mol%, more preferably at most 60 mol%, more preferably at most 40 mol%, more preferably at most 25 mol%, more preferably at most 10 mol%, and very particularly preferably at most 5 mol% of other structures or preferred structures (IIia) to (IIih) of formula (IIi), based on the sum of structures (IIi) (or (IIia) to (IIih)) and structure (II). Those skilled in the art will understand that the term "at most" can include 0 mol%, as this relates to other optional 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 "at most" here means more than 0 mol%.

[0098] Particularly preferably, the poly(urethane-co-carbonate) of the present invention comprises a structure of formula (I1), particularly having a 1,4-linkage, and / or a structure of formula (I2), and a structure of formula (II), wherein R 2 The 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.

[0099] Preferably, the thermoplastic poly(urethane-co-carbonate) of the present invention has 0 mol% to ≤39 mol%, more preferably 0 mol% to ≤37 mol%, even more preferably 0 mol% to 35 mol%, particularly preferably 0 mol% to 33 mol%, very particularly preferably 0 mol% to 5 mol%, and most preferably 0 mol% of 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 very 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. The aromatic content of the thermoplastic poly(urethane-co-carbonate) can be calculated by the stoichiometry of the starting materials. The aromaticity is preferably determined by...1 H-NMR spectroscopy is used for determination. Those skilled in the art can use this method to determine the proportion of polyurethanes composed of one or more aromatic diisocyanates, as well as the proportion of polycarbonate. 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 proton signals of polyurethanes and polycarbonate. From the proportion of polyurethane, its aromaticity can be determined by the molecular weight of the repeating unit of the polyurethane and the proportion of aromatics contained therein. This is a method known to those skilled in the art and is also preferred for determining the proportion of aromatic groups.

[0100] The thermoplastic poly(urethane-co-carbonate) of the present invention preferably comprises the structural 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 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 or branched, or may contain at least one ring, wherein the at least one ring may contain at least one heteroatom, 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 (IV). 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 The definition is shown in equation (IIi). m is the arithmetic mean of the repeating units, which is ≥ 4.0, preferably ≥ 4.5, particularly preferably ≥ 4.75, and very particularly preferably ≥ 5.0, and the wavy line represents the connection of the structure of formula (IV) in the poly(urethane-co-carbonate) chain. The arithmetic mean m of the repeating units is preferably ≤ 25.0, more preferably ≤ 21.0, and very more preferably ≤ 10.0.

[0101] Also preferred, and especially preferred, is that in formula (IV) group R2 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.

[0102] It will be apparent to those skilled in the art how the structure of formula (IV) is derived from the structures of formulas (I), (II), (Ii), and / or (IIi). Particularly preferred is formula (IVi) as follows. (IVi), Each R 1 R 2 The definitions of and m are shown in formula (IV). Those skilled in the art will understand that formula (IV) may also be randomly interrupted due to the presence of formulas (Ii) and / or (IIi). However, this polymer is particularly preferably free of the R group. 6 and R 7 .

[0103] Furthermore, preferably, the thermoplastic poly(urethane-co-carbonate) of the present invention preferably contains, in addition to the structure of formula (IV) or (IVi), 0 to 10% by weight, preferably 0.2 to 5% by weight, repeating units of formula (V). (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 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. The arithmetic mean n is a statistically derived number. Those skilled in the art can determine the proportion of groups in formula (IV) using their commonly used methods, such as NMR spectroscopy. This method may also depend on the properties of the monomers used.

[0104] Very particularly preferred, the thermoplastic poly(urethane-co-carbonate) inclusion structure of the present invention is of formula (VI). (VI) 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 R6 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 as 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 ≥ 4.0, preferably ≥ 4.5, more preferably ≥ 4.75, and very particularly preferably ≥ 5.0. x and 1-x are the relative ratios of the respective repeating units to each other. The arithmetic mean m of the repeating units is preferably ≤25.0, more preferably ≤21.0, and very particularly preferably ≤10.0. However, the polymer is most preferably free of R. 6 and R 7 Group.

[0105] Preferably, r is at least 1. Those skilled in the art can relate r to molecular weight. Clearly, when r is 1, formula (VI) 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 (VI). This results in r being greater than 1.

[0106] Those skilled in the art will understand that x must be less than 1. Those skilled in the art will understand that x must be ≤ 1. If unreacted diols are present, particularly diols of formula (Ia) and optionally diols of formula (X), then x is less than 1.

[0107] It will be apparent to those skilled in the art that the terminal group in formula (VI) is not necessarily a methyl group, but merely represents a potential end of the chain of formula (VI), or may be another connection point with other groups.

[0108] Those skilled in the art will understand the relationship between the method of the present invention and the thermoplastic poly(urethane-co-carbonate) of the present invention. In particular, those skilled in the art will understand the relationship between formulas (Ia) and (IIa) and formulas (I), (II), (III), (IIIa), (IV), (IVi), (V) and (VI).

[0109] The preferred feature of the method of the present invention is that the thermoplastic poly(urethane-co-carbonate) of the present invention can be prepared by this method in all embodiments, preferred embodiments, and combinations of preferred embodiments. Another aspect of the present invention provides a thermoplastic poly(urethane-co-carbonate) that can be obtained by the method of the present invention in all embodiments, preferred embodiments, and combinations of preferred embodiments. Preferably, it is the thermoplastic poly(urethane-co-carbonate) of the present invention.

[0110] Attached image: Figure 1 The GPC spectrum of the prepolymer (Example 4) based on TCD-DM and H12-MDI at a molar ratio of 1.25:1 (diol: diisocyanate) is plotted with molar mass on the x-axis. Figure 2 : A schematic diagram of the GPC spectrum of the prepolymer (Example 4), used to determine the arithmetic mean "m" of the repeating units of the prepolymer and the optional residual diol content. Names A to J represent individual peaks that must therefore be observed separately from each other. Figure 3 The GPC spectrum of the prepolymer (Example 3) of TCD-DM and H12-MDI in a molar ratio of 1.1:1 (diol: diisocyanate) is plotted with molar mass on the x-axis. Figure 4 : A schematic diagram of the GPC spectrum of the prepolymer (Example 3), used to determine the arithmetic mean "m" of the repeating units of the prepolymer and the optional residual diol content. Names A to K represent individual peaks that must therefore be observed separately from each other. Figure 5 : Poly(urethane-co-carbonate) based on TCD-DM and H12-MDI in a molar ratio of 1.25:1 (diol:diisocyanate) (Example 8) 13 C-NMR spectrum.

[0111] Example Materials used: Diol component (as shown in formula (Ia) according to the present invention) CHDM (Ia, 1) Cyclohexane-1,4-diethanol: a mixture of cis-cyclohexane-1,4-diethanol and trans-cyclohexane-1,4-diethanol, CAS: 105-08-8, 99%, Sigma Aldrich, Germany, for direct use without further purification. TCD-DM (Ia, 2) Tricyclodecanediethanol: a mixture of isomers, CAS: 26896-48-0, 96%, Sigma-Aldrich, Germany, used directly without further purification. Diisocyanate component (as shown in formula (IIa) according to the present invention) H12-MDI (IIa, 7) Dicyclohexylmethane-4,4'-diisocyanate (dicyclohexylmethane-2,4'-diisocyanate (≤ 10 wt%) and dicyclohexylmethane-2,2'-diisocyanate (≤ 2 wt%): a mixture of cis and trans isomers), CAS: 5124-30-1 (based on 4,4'-link), Covestro AG, Germany, for direct use without further purification. Carbonyl source (used to produce PUC from urethane diol prepolymers) DPC (Diphenyl Carbonate), CAS: 102-09-0, Covestro A, Germany, freshly distilled before use. Catalyst (used for the production of PUC from urethane diol prepolymers) Kat: Monobutyltin oxide, CAS: 2273-43-0, TIB Chemicals AG, Germany, for direct use without further purification.

[0112] Analysis method: GPC: The molar mass distribution was determined by gel permeation chromatography (GPC) by Currenta GmbH & Co. OHG. Approximately 30 mg of sample was weighed and dissolved in THF with gentle shaking for 2 hours. The sample was then filtered through a 0.45 µm PTFE filter and determined using a suitable GPC system equipped with an SDV column (e.g., PSS SDV 5 µm, PSS SDV 1000 Å, PSS SDV 100 Å, PSS SDV 50 Å). Calibration was performed using narrow-distribution polystyrene standards (for prepolymers, e.g., ReadyCalKit Polystyrene low, part number: PSS-PSKITR1L, nominal molecular weight 266-66000 Da; or for polymers, e.g., ReadyCal Kit Polystyrene, part number: PSS-PSKITR1, nominal molecular weight 474-2520000 Da), and adjusted according to the column and sample. Degassed THF was used as the eluent. The detection is performed using the refractive index detector (RI). This general method is defined in Currenta GmbH & Co. OHG AM 2011-0623701-09D, which is available upon request from Currenta.

[0113] Determination of the arithmetic mean m of the repeating units in the prepolymer of Example 4 In prepolymer synthesis, the diol component is always used in excess relative to the diisocyanate component. This results in the formation of oligomers with an arithmetic mean m of repeating units (see, for example, formula (III) or (IIIa)), and consequently, a certain proportion of the diol component remains in the mixture in an unreacted form (e.g., Figure 1 (GPC spectrum of Example 4 is shown).

[0114] It will be apparent to those skilled in the art that when the excess of the diol component is small, the accuracy of m determination by GPC is low because the higher oligomers (m ≥ 5) in the GPC spectrum will merge with each other due to the low resolution.

[0115] In these cases, it is not possible to explicitly allocate oligomers via GPC; therefore, the arithmetic mean m of the repeating units can only be approximately determined as a minimum (denoted by ">").

[0116] The determination of the arithmetic mean m of the repeating unit and the residual diol content is explained below approximately with reference to Example 4.

[0117] The m of the prepolymer and the residual unreacted diol (in weight percent) were determined using GPC spectra plotted with elution volume on the x-axis. Figure 1 In this process, each detected peak, if clearly defined, is assigned to an unreacted monomeric diol or oligomer based on its molecular weight. If the peaks are not clearly separated (as is often the case with longer-chain oligomers), it is preferable to divide them at the valley between the two peaks until no more valleys are measured (e.g., ...). Figure 2 (The GPC spectrum of Example 4 is shown).

[0118] Depend on Figure 2 The GPC spectrum of Example 4 yielded the following area F (in %): A: Prepolymer with repeating unit m = 6 (F = 58.6%) (This obviously also includes oligomers with higher repeating units, but the value is artificially described as "6") B: Prepolymer with repeating unit m = 5 (F = 8.9%) C: Prepolymer with repeating unit m = 4 (F = 8.6%) D: Prepolymer with repeating unit m = 3 (F = 8.4%) E: Prepolymer with repeating unit m = 2 (F = 7.6%) F: Prepolymer with repeating unit m = 1 (A = 5.7%) G: Unknown (F = 0.1%) H: Unknown (F = 0.2%) I: Unknown (F = 0.1%) J: Residual diol TCD-DM (F = 1.8%) m is determined based on the weighted arithmetic mean.

[0119] Where F (prepolymer) = 97.8% The arithmetic mean "m" of the repeating units in Example 4 is at least 4.9.

[0120] It will be apparent to those skilled in the art that when the excess of the diol component is very small (<25 mol%), m will increase and the proportion of unreacted monomeric diol will decrease. However, this also leads to poor GPC spectral resolution, making it difficult to accurately determine m by GPC, as shown in Example 3 (see Example 3). Figure 3 and Figure 4 ).

[0121] DSC: Glass transition temperature (T) g The value was determined by dynamic differential scanning calorimetry (DSC) according to standards DIN EN ISO 11357-1:2022-02 and DIN EN ISO 11357-2:2020-08, wherein the measurement was performed under nitrogen at a heating rate of 20 K / min and the inflection point during the second heating process was taken.

[0122] 13 C-NMR spectrum: pass 13 The ratio of urethane groups to carbonate groups in poly(urethane-co-carbonate) was determined by C-NMR spectroscopy. 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 HD600 NMR spectrometer.

[0123] Measurement parameters: Pulse program pulprog zgig30 Number of incremental scans per scan (NS): 512 Relaxation time D1 between two scans: 4 seconds The following example, Example 8, illustrates the evaluation of the ratio of urethane groups to carbonate groups in a poly(urethane-co-carbonate) produced from tricyclodecanediethanol (TCD-DM) and H12-MDI at a molar ratio of 1.25:1 (diol: diisocyanate). Reference is made here. Figure 5 .

[0124] Depend on13 C-NMR spectra are useful for determining the classification of carbamates and carbonates. The carbamate signal was at 156 ppm. The carbonate signal was at 155.6 ppm. The molar ratio is obtained directly from the area of ​​each signal normalized to 100.

[0125] Depend on Figure 5 In 13 The C-NMR spectroscopy yielded the following estimated molar ratio: Carbamate = 88 Carbonate = 12.

[0126] Hydroxyl value: The hydroxyl value (also known as the OH value) is determined by Currenta GmbH & Co. OHG using a titration method based on DIN EN ISO 4629-2. "Based on" means that pyridine is used instead of N-methyl-2-pyrrolidone as the base in the DIN EN ISO 4629-2 standard. The method used is defined in Currenta GmbH & Co. OHG's document 2011-0232602-92D, which is available upon request from Currenta.

[0127] NCO value: The NCO content was determined by titration according to DIN EN ISO 11909:2007-05.

[0128] Production of UDO (urethane diol prepolymer) Example 1: CHDM (as shown in formula (Ia, 1)) as the diol component reacts with H12-MDI (as shown in formula (IIa, 3)) as the diisocyanate structural unit in a molar ratio of 1.1:1 (diol: diisocyanate). 78.0 g (541 mmol) of CHDM was pre-added to a flask equipped with a reflux condenser and a dropping funnel. Trace amounts of air and water in the apparatus were then removed by alternating evacuation and nitrogen purging. The mixture was melted at 180 °C under nitrogen protection at standard pressure and stirred for 30 minutes. 129 g (492 mmol) of H12-MDI was added over several seconds via the dropping funnel. After 10 minutes, the temperature was increased to 200 °C and stirred for 30 minutes at 200 °C. The bath temperature was then increased to 220 °C and the mixture was stirred for another 30 minutes at 220 °C, after which the reaction was stopped. A slightly yellow, transparent prepolymer was obtained with an OH value of 25.1 mg KOH / g and a glass transition temperature T0. g The temperature is 106℃, and the molecular weight is M. nIt is 5780 g / mol.

[0129] Example 2: CHDM (as shown in formula (Ia, 1)) as the diol component reacts with H12-MDI (as shown in formula (IIa, 3)) as the diisocyanate structural unit in a molar ratio of 1.25:1 (diol: diisocyanate). 103.0 g (714 mmol) of CHDM was pre-added to a flask equipped with a reflux condenser and a dropping funnel. Trace amounts of air and water in the apparatus were then removed by alternating evacuation and nitrogen purging. Under nitrogen protection, the mixture was melted at 160 °C under standard pressure and stirred for 30 minutes. 150.0 g (572 mmol) of H12-MDI was added over several seconds via the dropping funnel. After 20 minutes, the temperature was increased to 180 °C, and the mixture was stirred at 180 °C for 30 minutes. After 30 minutes, a sample was taken under countercurrent nitrogen for NCO measurement. The reaction was stopped when the NCO value was 0%. A colorless, transparent prepolymer was obtained with an OH value of 62.8 mg KOH / g and a glass transition temperature T0. g The temperature is 97℃, and the molecular weight is M. n It is 2790 g / mol.

[0130] Example 3: TCD-DM (as shown in formula (Ia, 2)) as the diol component reacts with H12-MDI (as shown in formula (IIa, 3)) as the diisocyanate structural unit in a molar ratio of 1.1:1 (diol: diisocyanate). 107 g (545 mmol) of TCD-DM was pre-added to a flask equipped with a reflux condenser and a dropping funnel. Trace amounts of air and water in the apparatus were then removed by alternating evacuation and nitrogen purging. The mixture was melted at 200 °C under nitrogen protection at standard pressure and stirred for 30 minutes. 130 g (496 mmol) of H12-MDI was added over several seconds via the dropping funnel. The mixture was stirred at 200 °C for 30 minutes. The bath temperature was then increased to 220 °C, and the mixture was stirred at 220 °C for another 30 minutes, after which the reaction was stopped. A slightly yellow, transparent prepolymer was obtained with an OH value of 21.9 mg KOH / g and a glass transition temperature Tg. g The temperature was 128℃, and the molecular weight was M. n It is 4810 g / mol.

[0131] Example 4: TCD-DM (as shown in formula (Ia, 2)) as the diol component reacts with H12-MDI (as shown in formula (IIa, 3)) as the diisocyanate structural unit in a molar ratio of 1.25:1 (diol: diisocyanate). 112.2 g (572 mmol) of TCD-DM was pre-added to a flask equipped with a reflux condenser and a dropping funnel. Trace amounts of air and water in the apparatus were then removed by alternating evacuation and nitrogen purging. The mixture was melted at 200 °C under nitrogen protection at standard pressure and stirred for 30 minutes. 100.0 g (381 mmol) of H12-MDI was added over several seconds via the dropping funnel. The mixture was stirred at 200 °C for 60 minutes. After 60 minutes, the reaction was stopped. A slightly yellow, transparent prepolymer was obtained with an OH value of 54.5 mg KOH / g and a glass transition temperature T0. g The temperature is 104℃, and the molecular weight is M. n It is 2300 g / mol.

[0132] Table 1: Comparison of results from Examples 1 to 4 nb: Cannot be determined precisely, but is at least greater than 5 Polymers are produced by polycondensation of previously prepared urethane diol prepolymer (UDO) with diphenyl carbonate (DPC). (carbamate-co-carbonate)(PUC).

[0133] Example 5: In Example 1, the UDO component reacted with DPC, which served as a carbonyl source, in the presence of a catalyst at a molar ratio of 1:1.089 (UDO:DPC). 110.0 g (24.6 mmol, molar amount determined by measured OH value) of the product of Example 1, 5.74 g (26.8 mmol) of DPC, and 0.005 g (43 ppm based on the product of Example 1 and DPC) of catalyst were pre-added to a flask equipped with a Wiegler column and a distillation bridge. Trace amounts of air and water in the apparatus were then removed by alternating evacuation and nitrogen purging. The mixture was melted at 230 °C under nitrogen protection at standard pressure and stirred for 20 minutes. The temperature was then increased to 240 °C, and the pressure was reduced to 100 mbar over 20 minutes. During this process, phenol was continuously removed. The mixture was stirred at 100 mbar for approximately 10 minutes. Subsequently, the pressure was reduced to <1 mbar over 30 minutes, and stirring of the mixture continued for 60 minutes. The reaction was then stopped. A pale yellow, transparent polymer was obtained, whose M w It is 89200 g / mol, and the glass transition temperature T g The temperature was 130°C, and the molar ratio of carbonate to carbamate was 6:94. 4.2 g of distillate, mainly composed of phenol, was obtained (equivalent to 3.6 wt% of the product from Example 1 based on the starting material and DPC).

[0134] Example 6:In Example 2, the UDO component reacted with DPC, which served as a carbonyl source, in the presence of a catalyst at a molar ratio of 1:1.030 (UDO:DPC). 100.0 g (56.0 mmol, molar amount determined by measured OH value) of the product of Example 2, 12.36 g (57.7 mmol) of DPC, and 0.005 g (44 ppm based on the product and DPC of Example 2) of catalyst were pre-added to a flask equipped with a Wiegler column and a distillation bridge. Trace amounts of air and water in the apparatus were then removed by alternating evacuation and nitrogen purging. The mixture was melted at 190°C under nitrogen protection at standard pressure and stirred for 20 minutes. The pressure was then reduced to 100 mbar over 20 minutes. The mixture was stirred at 190°C for 10 minutes, at 200°C for 5 minutes, at 210°C for 5 minutes, at 220°C for 5 minutes, at 230°C for 20 minutes, and at 240°C for 5 minutes. During this process, phenol was continuously removed. The pressure was then reduced to <1 mbar over 25 minutes, and the mixture was stirred for another 60 minutes. The reaction of the mixture was then stopped. A pale yellow, transparent polymer was obtained, whose M... w It is 124700 g / mol, and the glass transition temperature T g The temperature was 121°C, and the molar ratio of carbonate to carbamate was 10:90. 10.9 g of distillate, mainly composed of phenol, was obtained (equivalent to 9.7 wt% based on the product of Example 2 and DPC from the starting materials).

[0135] Example 7: Example 3, as a component of UDO, reacted with DPC, as a carbonyl source, in the presence of a catalyst at a molar ratio of 1:1.098 (UDO:DPC). 110.0 g (21.5 mmol, molar amount determined by measured OH value) of the product of Example 3, 5.05 g (23.6 mmol) of DPC, and 0.005 g (43 ppm based on the starting material, product of Example 3, and DPC) of catalyst were pre-added to a flask equipped with a Wiegler column and a distillation bridge. Trace amounts of air and water in the apparatus were then removed by alternating evacuation and nitrogen purging. The mixture was melted at 240 °C under nitrogen protection at standard pressure and stirred for 20 minutes. The pressure was then reduced to <1 mbar over 45 minutes, and stirring of the mixture continued for 60 minutes. During this process, phenol was continuously removed. The reaction of the mixture was then stopped. A pale yellow, transparent polymer with M w It is 80800 g / mol, and the glass transition temperature T gThe temperature was 140°C, and the molar ratio of carbonate to carbamate was 5:95. 4.7 g of distillate, mainly composed of phenol, was obtained (equivalent to 4.1 g by weight based on the product of Example 3 and DPC from the starting materials).

[0136] Example 8: Example 4, as a component of UDO, reacted with DPC, as a carbonyl source, in the presence of a catalyst at a molar ratio of 1:1.041 (UDO:DPC). 110.0 g (53.4 mmol, molar amount determined by measured OH value) of the product of Example 4, 11.9 g (55.6 mmol) of DPC, and 0.005 g (41 ppm based on the product of Example 4 and DPC) of catalyst were pre-added to a flask equipped with a Wiegler column and a distillation bridge. Trace amounts of air and water in the apparatus were then removed by alternating evacuation and nitrogen purging. The mixture was melted and stirred for 20 minutes at standard pressure under nitrogen protection at 220°C. The pressure was then reduced to 100 mbar over 10 minutes. The mixture was stirred at 220°C for 15 minutes, at 230°C for 15 minutes, and at 240°C for 10 minutes. During this process, phenol was continuously removed. Subsequently, the pressure was reduced to <1 mbar over 35 minutes, and the mixture was stirred for another 60 minutes. The reaction was then stopped. A pale yellow, transparent polymer was obtained, whose M... w It is 81200 g / mol, and the glass transition temperature T g The temperature was 122°C, and the molar ratio of carbonate to carbamate was 12:88. 9.7 g of distillate, mainly composed of phenol, was obtained (equivalent to 8.0 wt% of the product from Example 4 based on the starting materials and DPC).

[0137] Table 2: Comparison of results from Examples 5 to 8 Example UDO (urethane diol) <![CDATA[M w (g / mol)]]> <![CDATA[T g (℃)]]> Molar ratio (carbonate:carbamate) Distillate (weight %)* impression** 5 E Example 1 89200 130 6:94 3.6 ductility 6 E Example 2 124700 121 10:90 9.7 ductility 7 E Example 3 80800 140 5:95 4.1 ductility 8 E Example 4 81200 122 12:88 8.0 ductility *Based on starting material prepolymer and diphenyl carbonate A preliminary impression can be obtained by bending a solidified melt by hand. If it does not break, the material is described as "ductile"; otherwise, it is described as "brittle".

[0138] Production of poly(urethane-co-carbonate) (PUC) – Continuous One-Pot Process Example 9: CHDM (as shown in formula (Ia, 1)) as a diol component reacts with H12-MDI (as shown in formula (IIa, 3)) as a diisocyanate structural unit in a molar ratio of 1.1:1 (diol: diisocyanate), and then reacts with DPC as a carbonyl source in a molar ratio of 1.1:1:0.103 (diol: diisocyanate: DPC), with a catalyst added.

[0139] 43.0 g (298 mmol) of CHDM was pre-added to a flask equipped with a Wiegler column, distillation bridge, and dropping funnel. Trace amounts of air and water in the apparatus were then removed by alternating evacuation and nitrogen purging. The CHDM was melted at 200 °C under nitrogen protection at standard pressure and stirred for 30 min. 71.0 g (271 mmol) of H12-MDI was added over several seconds via the dropping funnel. The mixture was stirred at 200 °C for 25 min, at 220 °C for 25 min, at 230 °C for 10 min, and at 240 °C for 5 min. 5.95 g (28 mmol) of DPC and 0.005 g (42 ppm based on the starting materials CHDM, H12-MDI, and DPC) of catalyst were added countercurrently under nitrogen. The pressure was then reduced to continuously remove phenol. For this purpose, the pressure was reduced to <1 mbar over 60 min, and the mixture continued to condense for 30 min. The reaction was then stopped. A light yellow, transparent polymer was obtained, whose M... w It is 55600 g / mol, and the glass transition temperature T g The temperature was 131°C, and the molar ratio of carbonate to carbamate was 5:95. 4.9 g of distillate, mainly composed of phenol, was obtained (equivalent to 3.9 wt% based on the starting materials CHDM, H12-MDI, and DPC).

Claims

1. A method for producing thermoplastic poly(urethane-co-carbonate), comprising the following steps: (i) Making at least one aliphatic diol of formula (Ia) (him) Where each R in equation (Ia) 1 Each of the components is an aliphatic group having 4 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) (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 1.30:1.0 to 1.01:1.

0.

2. The method as described in claim 1, characterized in that, In step (i), a diol of formula (X) and / or a diisocyanate of formula (Xi) are also used. HO-R 6 -OH (X), Each R 6 The alkylene group is an aliphatic alkylene group having 4 to 20, preferably 5 to 18, more preferably 6 to 16 carbon atoms. This 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 when R... 6 When at least one ring is involved, at least one OH group is not a primary alcohol group. OCN-R 7 -NCO (Xi), Where each R in equation (Xi) 7 yes - Straight-chain alkylene compounds containing 4 to 12 carbon atoms, - Contains 5 to 20, preferably 7 to 18, cyclic aliphatic groups, wherein the structure R 7 The connection with at least one nitrogen atom shown in structure (Xi) is made via a primary carbon atom, or - Aromatic groups containing 6 to 18 carbon atoms.

3. Carbamate diol prepolymers having the structure of formula (III) Where each R in equation (III) 1 Each of the groups is an aliphatic group having 4 to 18 carbon atoms, comprising at least one ring, wherein the ring may optionally comprise at least one heteroatom, and wherein the -CH2-R group enclosed in 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 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 It does not incorporate into the poly(urethane-co-carbonate) chain via CH2- groups on at least one side. and Where each R in equation (III) 2 It is a bridged aliphatic structure having 6 to 18 carbon atoms, wherein the bridged structure comprises at least one ring, and wherein the ring may optionally comprise at least one heteroatom, and wherein the connection between the bridged structure and the nitrogen atom shown in formula (III) is made via secondary or tertiary carbon atoms; and wherein R is expressed as 2 / R 7 Represents group R 2 At least sometimes they can be independent of each other as R 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 containing 6 to 18 carbon atoms, Where m is the arithmetic mean of the repeating units and is a number ≥ 4.

4. The urethane diol prepolymer according to claim 3, characterized in that, The urethane diol prepolymer has an OH value of 14 to 85 mg KOH / g determined by titration according to DIN EN ISO 4629-2, where "based on" means that pyridine is used instead of N-methyl-2-pyrrolidone as the base.

5. The urethane diol prepolymer as described in claim 3 or 4, characterized in that, The glass transition temperature (Tg) of the urethane diol prepolymer is ≥80℃, wherein the glass transition temperature is determined by dynamic differential scanning calorimetry.

6. The urethane diol prepolymer according to any one of claims 3 to 5, characterized in that, The urethane diol prepolymer is prepared by method step (i) of the method as described in any one of claims 1 or 2.

7. The urethane diol prepolymer according to any one of claims 3 to 6, characterized in that, The number-average molecular weight of the urethane diol prepolymer, as determined by gel permeation chromatography in tetrahydrofuran using polystyrene as a standard, is between 1500 and 10000 g / mol.

8. Thermoplastic poly(urethane-co-carbonate), comprising structures of formulas (I) and (II), (I)， Where each R in equation (I) 1 Each of the groups is an aliphatic group having 4 to 18 carbon atoms, comprising at least one ring, and the ring may optionally comprise at least one heteroatom; (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 ≥1 mol% to ≤15 mol% 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.

9. The thermoplastic poly(urethane-co-carbonate) as described in claim 8, characterized in that, It does not contain ether groups and / or ester groups.

10. The thermoplastic poly(urethane-co-carbonate) as described in claim 8 or 9, characterized in that, The thermoplastic poly(urethane-co-carbonate) contains up to 39 mol%, preferably up to 5 mol%, of aromatic groups, wherein these amounts are based on the total amount of aliphatic and aromatic groups.

11. The thermoplastic poly(urethane-co-carbonate) according to any one of claims 8 to 10, comprising the structural 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 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 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 It does not incorporate into the poly(urethane-co-carbonate) chain via CH2- groups on at least one side. 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 (IV) is made via a primary carbon atom, or - An aromatic group containing 6 to 18 carbon atoms, and m is the arithmetic mean of the repeating units, and is a number ≥ 4. The wavy line represents the connection of the structure of formula (IV) in the poly(urethane-co-carbonate) chain.

12. The thermoplastic poly(urethane-co-carbonate) according to any one of claims 8 to 11, characterized in that, The thermoplastic poly(urethane-co-carbonate) has a glass transition temperature ≥110℃ as determined by dynamic differential scanning calorimetry.

13. The thermoplastic poly(urethane-co-carbonate) according to any one of claims 8 to 12, characterized in that, The weight-average molar mass of the thermoplastic poly(urethane-co-carbonate) is up to 190,000 g / mol.

14. The thermoplastic poly(urethane-co-carbonate) according to any one of claims 8 to 12, characterized in that, It is produced by the method described in claim 1 or 2.

15. The method of claim 1 or 2, or the urethane diol prepolymer of any one of claims 3 to 7, or the thermoplastic poly(urethane-co-carbonate) of any one of claims 8 to 13, characterized in that, R in equation (Ia), equation (I), equation (III) or equation (IV) 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 formulas (Ia), (I), (III) or (IV).

16. The method of claim 1 or 2, or the urethane diol prepolymer of any one of claims 3 to 7, or the thermoplastic poly(urethane-co-carbonate) of any one of claims 8 to 13, characterized in that, Structure R in equations (IIa), (II), (III) or (IV) 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 equations (IIa), (II), (III) or (IV); 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.

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