Furane-containing polymers

Abstract

The present invention relates to furane-containing polymers, and to precursors for producing these furane-containing polymers and processes for producing both the polymers and the precursors. The invention inter alia discloses hydroxymethylfurane-carbonitrile self-condensates as well as polyesters, polyesteramides and polyurethanes which can be obtained from 5-hydroxymethyl-2-furfural.

Description

[0001]UNIVERSITY OF BIELEFELD Düsseldorf, 3 September 2024 Our reference: UD 42233 / SAM ───────────────────────────────────────────────────────────────── Bielefeld University Universitätsstraße 25, 33615 Bielefeld, Germany ─ ... ─────────────────────────────────────────────────────────────────────── Description The present invention relates to furan-containing polymers, as well as precursors for the preparation of these furan-containing polymers and preparation processes for both the polymers and the precursors. In recent years, due to the urgency of the environmental problems associated with conventional polymers, such as the fact that they are made from petroleum, i.e. non-renewable raw materials, numerous attempts have been made to replace the polymers previously used in industry and in everyday life with alternatives based on renewable raw materials.In particular, polymers containing furan are considered here, since an important starting material for these polymers, 5-hydroxymethyl-2-furfural (5-HMF), can be produced from carbohydrates. 5-HMF is accessible from D-fructose, which in turn is obtainable by isomerization starting from the readily available and inexpensive sugar D-glucose. However, there is still a need for furan-containing polymers and processes for producing them, and the skilled person is faced with the task of providing further polymers, precursors therefor, and processes for producing these substances. This object is achieved by a polymer according to claim 1. Accordingly, a polymer comprising the structure (I) is provided. in the repeating unit, where X is selected from a) -C(=NH)-O- b) -CH2-OC(=O)-YC(=O)-O- c) -CH2-OC(=O)-YC(=O)-NH- d) where Y is each independently selected substituted or unsubstituted C1 to C6 alkylene, alkenylene, and alkynylene, where the substituents are selected from hydroxyl and aryl. Z is each independently selected substituted or unsubstituted C2 to C6 alkylene, alkenylene, and alkynylene, phenylene, Ph-(CH2)k-Ph (where k=1 to 6), and furan, where the substituents are selected from hydroxyl, aryl, and C1 to C6 alkylene; and W is selected from Z and -NH-Z-NH-. It has been found that these novel polymers have outstanding properties that appear to have potential for a wide range of applications. The present invention thus also relates to a use of the polymers according to the invention for one or more of the following areas of application: - composite materials - materials for pipes or profiles, packaging - foams - bioadhesives - textile materials - coating materials, in particular paints.- Light scavenger in the solar industry - Materials for printing ink or graphic applications - Packaging material. Y is preferably selected from C2 to C4 alkylene. Z is preferably selected from substituted or unsubstituted C2 to C6 alkylene, alkenylene and alkynylene, phenylene, Ph-(CH2). k -Ph (where k=1 to 6) and furan, wherein the substituents are selected from hydroxyl and aryl. More preferably, Z is selected from substituted or unsubstituted phenyl or Ph-(CH2) k -Ph (where k=2, 4, 5, and 6). Z is further preferably selected from C2 to C6 alkylene. The present invention also relates to compounds of the following structure: where R 1 is selected from CH2OH, CH2NH2, C(=N-OR 3 )H, CHO and CN with R 3 = H or C1 to C6 linear, branched or cyclic alkyl. R is preferably 1 selected from CH2OH, CH2NH2, C(=N-OR 3)H and CN. These compounds can serve as precursor materials for the preparation of the polymers according to the invention. In the context of the present invention, the structural unit in particular a chemical single bond to another structural unit within the same molecule. Within the present application, the abbreviations (= Y, Z, R n etc.) always have the same chemical structures, unless otherwise stated. According to a preferred embodiment of the invention, the polymer comprises at least one section in which structure (I) forms the repeating unit. According to a preferred embodiment, the polymer consists of repeating units of structure (I), ie, it has the following structure (III): where n is preferably at least 10, more preferably from ≥ 5 to ≤ 2,500, even more preferably from ≥ 20 to ≤ 2,000, and most preferably from ≥ 50 to ≤ 2,000. According to a preferred embodiment, the polymer according to the invention, in particular the polymer according to structure (III), has an average molecular weight of at least 3,000, more preferably from ≥ 3,000 to ≤ 1,000,000, even more preferably from ≥ 5,000 to ≤ 800,000, and most preferably from ≥ 25,000 to ≤ 500,000. This can be measured by gel permeation chromatography. Preferred embodiments of the invention are discussed below: According to a preferred embodiment of the invention, a polymer is provided comprising the structure (IV) in the repeating unit: According to a preferred embodiment of the invention, the polymer comprises at least one section in which structure (IV) forms the repeating unit. According to a preferred embodiment, the polymer consists of repeating units of structure (IV), i.e., it has the following structure (V): where n is preferably at least 10, more preferably from ≥ 5 to ≤ 2,500, even more preferably from ≥ 20 to ≤ 2,000, and most preferably from ≥ 50 to ≤ 2,000. According to a preferred embodiment, the polymer consists of structure (V) and has an average molecular weight of at least 3,000, more preferably from ≥ 3,000 to ≤ 1,000,000, even more preferably from ≥ 5,000 to ≤ 800,000, and most preferably from ≥ 25,000 to ≤ 500,000. This can be measured by gel permeation chromatography. The present invention further comprises a process for preparing a polymer of structure (V), comprising the preparation and polymerization of 5-(hydroxymethyl)furan-2-carbonitrile. Surprisingly, it has been found that this polymer can be prepared in a simple manner, in particular while avoiding the otherwise commonly used HCl.According to a preferred embodiment of the invention, the polymerization takes place at a pressure of ≤ 40 mbar and a temperature of ≥ 50 ° C, preferably at a pressure of ≥ 20 mbar and ≤ 40 mbar and a temperature of ≥ 50 ° C and ≤ 200 ° C. According to an alternative preferred embodiment of the invention, the polymerization takes place at a pressure of ≥ 1 bar and ≤ 3 bar and a temperature of ≥ 80 ° C, preferably at a temperature of ≥ 100 ° C and ≤ 230 ° C. The glass transition temperature and molar mass distribution can be easily adjusted via the polymerization conditions, which offers the advantage that the properties of the polymer obtained can be tailored to the respective application. According to a preferred embodiment of the invention, the use of a polymer according to structure (IV) comprises one or more of the following areas of application: - textile materials - coating materials, in particular paints.- "light scavenger" in the solar industry - materials for printing ink or graphic applications - packaging material According to a preferred embodiment of the invention, a polymer is provided comprising the structure (VI) in the repeating unit:. According to a preferred embodiment of the invention, the polymer comprises at least one section in which structure (VI) forms the repeating unit. According to a preferred embodiment, the polymer consists of repeating units of structure (VI), ie it has the following structure (VII): where n is preferably at least 10, more preferably from ≥ 5 to ≤ 2,500, more preferably from ≥ 20 to ≤ 2,000, and most preferably from ≥ 50 to ≤ 2,000. According to a preferred embodiment, the polymer consists of structure (VII) and has an average molecular weight of at least 3,000, more preferably from ≥ 3,000 to ≤ 1,000,000, more preferably from ≥ 5,000 to ≤ 800,000, and most preferably from ≥ 25,000 to ≤ 500,000. This can be measured by gel permeation chromatography.According to a preferred embodiment of the invention, the use of a polymer according to structure (VII) comprises one or more of the following areas of application: - composite materials - materials for pipes or profiles, packaging - foams - bioadhesives - textile materials - coating materials, in particular varnishes - light scavengers in the solar industry - materials for printing ink or graphic applications - packaging material The present invention relates to a process for the preparation of polymers of structure (VII) comprising the polymerization of compounds of the following structure (VIII):. at a pressure of ≤ 0.25 mbar and a temperature of ≥ 50°C, preferably at a pressure of ≥ 0.05 mbar and ≤ 0.25 mbar and a temperature of ≥ 50°C and ≤ 200°C. Surprisingly, it has been found that a polymer with excellent properties, in particular with regard to the glass transition temperature, the molecular weight and / or the melting temperature, can be produced in this way. The production of compounds of structure (VIII) can be easily realized on a larger scale in many applications, which can be advantageous for industrial-scale applications. According to one embodiment of the invention, the polymerization can be carried out without further additives. According to an alternative embodiment of the invention, ≥ 0.1% to ≤ 2% (in each case mol:mol, based on the precursor substance) of an acid or an acidic catalyst is added.Alternatively, a biocatalyst can also be used as the catalyst component, with an immobilized lipase being used preferably here. Lipase B from Candida antarctica in immobilized form is particularly suitable for the production of polyamides and polyesters. According to a preferred embodiment of the invention, a process for producing polymers of structure (VII) comprises the following steps: a) Reaction of 5-HMF with a suitable precursor substance to obtain a compound according to structure (IX):. b) Reduction to obtain a compound of structure (VIII). The following compounds of structures (VIIIa), (IXa), and (IXb) can also be used as alternative precursors: (VIIIa) According to a preferred embodiment of the invention, there is provided a polymer comprising the structure (X) in the repeating unit: According to a preferred embodiment of the invention, the polymer comprises at least one section in which the structure (X) forms the repeating unit. According to a preferred embodiment, the polymer consists of repeating units of structure (X), ie it has the following structure (XI): where n is preferably at least 10, more preferably from ≥ 5 to ≤ 2,500, more preferably from ≥ 20 to ≤ 2,000, and most preferably from ≥ 50 to ≤ 2,000. According to a preferred embodiment, the polymer consists of the structure (XI) and has an average molecular weight of at least 3,000, more preferably from ≥ 3,000 to ≤ 1,000,000, more preferably from ≥ 5,000 to ≤ 800,000, and most preferably from ≥ 25,000 to ≤ 500,000. This can be measured by gel permeation chromatography.According to a preferred embodiment of the invention, the use of a polymer according to structure (XI) comprises one or more of the following areas of application: - composite materials - materials for pipes or profiles, packaging - foams - bioadhesives - textile materials - coating materials, in particular varnishes - light scavengers in the solar industry - materials for printing ink or graphic applications - packaging material The present invention relates to a process for the preparation of polymers of structure (XI) comprising the polymerization of compounds of the following structure (XII):. at a pressure of ≤ 0.25 mbar and a temperature of ≥ 100°C, preferably at a pressure of ≥ 0.05 mbar and ≤ 0.25 mbar and a temperature of ≥ 100°C and ≤ 200°C. Surprisingly, it was found that a polymer with excellent properties, particularly with regard to the glass transition temperature, molecular weight, and / or melting temperature, can be produced in this way. The following compound of structure (XIIa) can also preferably be used as an alternative precursor substance: The compounds of structure (XII) can be easily prepared by reduction of the corresponding compounds of structure (XIII): which in turn are accessible from 5-(hydroxymethyl)-furan-2-carbonitrile. Alternatively, the compounds of structure (XII) can be prepared simply by reducing the corresponding compounds of structure (XIV): These, in turn, are accessible from 5-(hydroxymethyl)furfural, e.g., via structure (IX). Alternatively, a compound with structure (IX) can also be directly reductively aminated to obtain the corresponding amines of type (XII). In choosing the method for reductive amination, the skilled person can resort to both chemical processes (such as the Leuckart-Wallach reaction) and enzymatic processes, preferably using a transaminase or amine dehydrogenase.Thus, according to a preferred embodiment of the present invention, a process for preparing the polymer having structure (XI) comprises the following steps: a) reacting 5-(hydroxymethyl)furfural to form a compound of structure (IX); b) optionally converting the compound of structure (IX) to a compound having structure (XIII) or (XIV) c) reductive amination or reduction to obtain a compound of structure (XII); d) polymerization According to a preferred embodiment of the invention, a polymer is provided comprising structure (XV) in the repeating unit:. According to a preferred embodiment of the invention, the polymer comprises at least one section in which structure (XV) forms the repeating unit. According to a preferred embodiment, the polymer consists of repeating units of structure (XV), ie, it has the following structure (XVI): where n is preferably at least 10, more preferably from ≥ 5 to ≤ 2,500, even more preferably from ≥ 20 to ≤ 2,000, and most preferably from ≥ 50 to ≤ 2,000. According to a preferred embodiment, the polymer consists of structure (XVI) and has an average molecular weight of at least 3,000, more preferably from ≥ 3,000 to ≤ 1,000,000, even more preferably from ≥ 5,000 to ≤ 800,000, and most preferably from ≥ 25,000 to ≤ 500,000. This can be measured by gel permeation chromatography. According to a preferred embodiment of the invention, the use of a polymer according to structure (XVI) comprises one or more of the following areas of application: - composite materials, in particular foams - materials for pipes or profiles, packaging - foams - bioadhesives - textile materials - coating materials, in particular paints.- "light scavenger" in the solar industry - materials for printing ink or graphic applications - packaging material The present invention also relates to a production process for producing polymers of the structure (XVI), comprising the reaction of a precursor substance of the structure (XVII):. with a suitable further precursor substance, preferably of the structure OCN-Z-NCO or of the structure R 4 OC(=O)-ZC(=O)-OR 4 , with R 4selected from H or C1 to C6 alkyl. It has been found that suitable polymers can be prepared in this way. The compounds of structure (XVII) can in turn be obtained by reacting 5-hydroxymethylfurfural with H2N-Z-NH2. According to a preferred embodiment of the invention, a polymer is provided comprising the structure (XVIII) in the repeating unit: (XVIII) According to a preferred embodiment of the invention, the polymer comprises at least one section in which the structure (XVIII) forms the repeating unit. According to a preferred embodiment, the polymer consists of repeating units of structure (XVIII), ie, it has the following structure (XIX): where n is preferably at least 10, more preferably from ≥ 10 to ≤ 2,500, even more preferably from ≥ 50 to ≤ 2,000, and most preferably from ≥ 100 to ≤ 2,000. According to a preferred embodiment, the polymer consists of the structure (XIX) and has an average molecular weight of at least 3,000, more preferably from ≥ 3,000 to ≤ 1,000,000, even more preferably from ≥ 5,000 to ≤ 800,000, and most preferably from ≥ 25,000 to ≤ 500,000. This can be measured by gel permeation chromatography. According to a preferred embodiment of the invention, the use of a polymer according to the structure (XIX) comprises one or more of the following areas of application: - composite materials - materials for pipes or profiles, packaging - foams - bioadhesives - textile materials - coating materials, in particular paints.- "light scavenger" in the solar industry - materials for printing ink or graphic applications - packaging material The present invention also relates to a production process for producing polymers of the structure (XIX), comprising the reaction of a precursor substance of the structure (XX): with a suitable further precursor substance, preferably of the structure OCN-Z- or of the structure R. 4 OC(=O)-ZC(=O)-OR 4 , with R 4selected from H or C1 to C6-alkyl It has been found that suitable polymers can be prepared in this way. The compounds of structure (XX) can in turn be obtained by reducing the compounds of structure (XVII). The components to be used according to the invention, as well as those claimed and described in the exemplary embodiments, are not subject to any special exceptional conditions with regard to their size, shape, choice of material and technical conception, so that the selection criteria known in the field of application can be applied without restriction. Further details, features and advantages of the subject matter of the invention emerge from the subclaims and from the following examples, which are purely illustrative and not to be regarded as restrictive. The description of syntheses known from the literature is omitted.Synthesis of the precursor compound 5-(Hydroxymethyl)-furan-2-carbonitrile Precursor 1: Synthesis of 5-(Hydroxymethyl)-furan-2-carbaldehyde oxime: 1 mol of the aldehyde compound is mixed with 1.2 mol of hydroxylamine dissolved in water (50% w / w). Stir for 30 minutes to obtain the corresponding E / Z aldoxime. Extract with ethyl acetate, wash with brine, and dry over solid MgSO4. The solvent is removed under reduced pressure. Reaction scale: 30 g (238 mmol), isolated yield: 99%, purity: 95%, yellow solid. Z-isomer: 69%. 1 H NMR (500 MHz, CD2Cl2) δ 7.99 (s, 1H), 6.60 (d, J = 3.5 Hz, 1H), 6.39 (d, J = 3.5 Hz, 1H), 4.63 (s, 2H). E isomer: 31%: 1H NMR (500 MHz, CD2Cl2) δ 7.47 (s, 1H), 7.25 (d, J = 3.5 Hz, 1H), 6.46 (d, J = 3.5 Hz, 1H), 4.64 (s, 2H). Precursor 2: Synthesis of (5-((Hydroxyimino)methyl)-furan-2-yl)-methyl acetate: 7.1 mmol of 5-(hydroxymethyl)-furan-2-carbaldehyde oxime was stirred with 5 ml of MtBE, 10% (w / w) immobilized lipase B from Candida antarctica (iCALB), and 1.1 equivalents of vinyl acetate for 30 minutes at 40°C. After filtration, the solvent was evaporated under reduced pressure. Isolated yield: >99%, purity: 94%, orange oil. Z-isomer 41%: 1 H NMR (500 MHz, CD2Cl2) δ 8.01 (s, 1H), 6.64 (t, J = 3.7 Hz, 1H), 6.52 (d, J = 3.4 Hz, 1H), 5.10 (d, J = 7.1 Hz, 2H), 2.11 (s, 3H). E isomer 59%: 1H NMR (500 MHz, CD2Cl2) δ 7.52 (s, 1H), 7.32 (d, J = 3.4 Hz, 1H), 6.59 (d, J = 3.5 Hz, 1H), 5.10 (s, 2H), 2.11 (s, 3H). Synthesis of 5-(hydroxymethyl)-furan-2-carbonitrile on a 10 g scale under optimized conditions. 3.25 g of Cu(II)OAc (18 mmol) was dissolved in 200 mL of MeCN and heated to 80°C. 10 g of precursor 1 (71 mmol) was dissolved in 0.8 L of MeCN and added dropwise at 80°C over 3 hours. The gray suspension was filtered and extracted with ethyl acetate. The mixture was washed with brine and dried over MgSO4. The solvent was evaporated at 40°C and 340 mbar to obtain a yellow oil. Yield: 65% nitrile, 3% amide. The crude product was purified by silica gel column chromatography (EtOAc:cyclohexane 9:1). 5-Hydroxymethyl-2-carbonitrile: 1 H NMR (500 MHz, CD2Cl2) δ 7.13 (d, J = 3.5 Hz, 1H), 6.50 – 6.45 (m, 1H), 4.67 (d, J = 5.8 Hz, 2H). 5-Hydroxymethyl-2-carbamide: 1H NMR (500 MHz, DMSO) δ 7.03 (d, J = 3.3 Hz, 1H), 6.41 (d, J = 3.4 Hz, 1H), 4.43 (s, 2H). Enzymatic synthesis of 5-(hydroxymethyl)-furan-2-carbonitrile under optimized conditions. 200 mg of precursor 1 (14 mM, 2 g / L), 50 g / L of Oxd RE M29G whole-cell catalyst (wet cell concentration), 50 mM potassium phosphate buffer with a pH of 7 at 10°C, and a total reaction volume of 100 ml were mixed. After 24 hours of reaction (100% conversion), another 200 mg of precursor 1 was added to the same enzyme solution, resulting in a conversion rate of 93% after the same time. It is extracted with dichloromethane, and the solvent is distilled under vacuum. Yield: 93%. 1 H NMR (500 MHz, DMSO) δ 7.53 (d, J = 1.5 Hz, 1H), 6.59 (d, J = 3.6 Hz, 1H), 5.57 (s, 1H), 4.47 (s, 2H). FTIR: ^ [cm -1] = 3420, 3135, 2930, 2870, 2230, 1519, 1012 Synthesis of polymethylfuranimidate (structure (V)): Synthesis 1: 5-(Hydroxymethyl)-furan-2-carbonitrile is heated for 5 h at 150 °C and 30 mbar to form a polymer. Glass transition temperature = 95 °C, decomposition temperature (5%) = 272 °C FTIR (PMFI (1)): ^ [cm -1 ] = 3298 (v -OH- residue alcohol, 3180 (v(-C=C-) furan), 1504 (d(C=C) furan), 2300 (v C#N, residue nitrile), 1648 (v C=N, imine), 1207 (v COC, (imido)ester). Characteristic broad band between 3500 – 2000 cm -1(Hydrogen bonds, imine) Synthesis 2: 5-(Hydroxymethyl)-furan-2-carbonitrile is heated for 3 h at 60 °C and 30 mbar. Glass transition temperature = 28 °C, decomposition temperature (5%) = 149 °C. Synthesis 3: 5-(Hydroxymethyl)-furan-2-carbonitrile is heated for 3 h at 100 °C and 1 atm. Glass transition temperature = 70 °C, decomposition temperature (5%) = 154 °C. Synthesis 4: 5-(Hydroxymethyl)-furan-2-carbonitrile is heated for 3 h at 120 °C and 1 atm. Glass transition temperature = 70 °C, decomposition temperature (5%) = 144 °C. Synthesis 5: 5-(Hydroxymethyl)-furan-2-carbonitrile is heated for 5 h at 100 °C to 230 °C and 30 mbar. Synthesis 6: 5-(Hydroxymethyl)-furan-2-carbonitrile is heated for 3 h at 100 °C to 190 °C and 30 mbar. Synthesis 7: 5-(Hydroxymethyl)-furan-2-carbonitrile is heated for 1-6 h at 150 °C and 30 mbar. Properties for Synthesis 5-7: A brown, highly viscous liquid to a brown solid is obtained. FTIR: ^ [cm -1] = 3460, 3152, 2929, 2880, 1658, 1606, 1540, 1213, 1025 Modification of the glass transition temperature as a function of the polymerization temperature at a fixed polymerization time of 3 hours. *Gradually from 100°C – 230°C within 5h. Polymerization temperature [°C] Glass transition temperature [°C] 100 -22 120 -14 140 4 150 12 170 26 190 40 230* 90 Modification of the glass transition temperature as a function of the polymerization time at a fixed temperature of 150°C. Polymerization time [min] Glass transition temperature [°C] 0.5 -58 1 -33 2 2 3 15 4 22 5 32 6 40 Molar mass distribution as a function of polymerization time and polymerization temperature. Temperature Time [h] Mn [g / mol] Mw [g / mol] Mw / Mn n [°C] 120 3 455 504 1.1 4 140 3 1016 1486 1.5 8 160 3 1654 2469 1.5 13 150 1 638 785 1.2 5 150 2 2764 3470 1.3 22 150 3 3368 12544 3.7 27 150 4 4612 69784 15 37 Synthesis of polymer of structure (VII) with Y = C2H4 A) Synthesis of the precursor substance (structure (VIII) with Y = C2H4) Variant 1: One-pot synthesis 5.58 g of 5-HMF (44.3 mmol) and 4.42 g of succinic anhydride (44.2 mmol) are dissolved in 5 ml of MTHF and refluxed overnight. The solution is cooled to 0°C in an ice bath, and 50 ml of MTHF is added. 2 g of NaBH4 (1.2 Na eq.) are added successively to the solution over 5 min, and the suspension is stirred at room temperature overnight. After removal of the solvent in vacuo, the colorless solid is dissolved in 50 ml of MQ water while cooling in an ice bath. The basic aqueous solution (pH = 9) is extracted twice with 20 ml of MTHF. After phase separation, the aqueous solution is acidified to pH < 4 using 1 M HCl and ice-bath cooling. A colorless solid precipitates. The solid is filtered through a fluted filter, and the aqueous phase is transferred to a separatory funnel.The solid is then washed with 50 ml of MTHF, whereupon it dissolves and forms the organic phase as a yellow liquid in the separating funnel. After phase separation, the organic phase is dried over MgSO4 and reduced at 40°C and 250 mbar. A colorless solid is obtained. Yield: 97% Alternative reduction procedure: 5.3 g (23.5 mmol) of 4-((5-formylfuran-2-yl)methoxy)-4-oxobutanoic acid is dissolved in 60 ml of ethyl acetate, and 1.1 g of sodium equivalent of NaBH4 is added portionwise over 5 minutes while cooling with an ice bath. The suspension is stirred for a further 3 hours at room temperature, and the solvent is then evaporated off at 250 mbar and 40°C. While cooling with an ice bath and stirring continuously, 40 ml of distilled water is slowly added. The basic solution is extracted with 30 ml of MTHF, and the aqueous phase is then acidified with 1 N HCl to pH < 4 while continuously cooling in an ice bath. A colorless solid precipitates, which is washed with 20 ml of MTHF.The acidic aqueous solution was extracted once with 50 ml of MTHF. After phase separation, the organic phases were combined, dried over MgSO4, and reduced at 40°C and 150 mbar to obtain a colorless solid. Yield: 91%. 1H NMR (500 MHz, DMSO) δ 12.23 (s, 1H), 6.44 (d, J = 3.2 Hz, 1H), 6.27 (d, J = 3.1 Hz, 1H), 5.25 (s, 1H), 5.02 (s, 2H), 4.38 (s, 2H), 2.53 (dd, J = 7.3, 4.7 Hz, 2H), 2.48 (dd, J = 7.2, 4.6 Hz, 2H). Alternative reaction procedure on a pilot scale: 553 g of 5-HMF (4.4 mol) and 439 g of succinic anhydride (4.4 mol) are dissolved in 500 milliliters of 2-methyltetrahydrofuran (MTHF). The mixture is heated under reflux for 19 hours. After cooling to 50 °C, the precipitated precursor is dissolved in a mixture of 80% ethyl acetate (EtOAc) and 20% methanol (MeOH) to achieve a substrate concentration of 125 grams per liter (g / L). While cooling in an ice bath, 50 g of sodium borohydride (NaBH4) is added over 20 minutes. After 1 hour, 5M hydrochloric acid (HCl) is added gradually until a pH of 1 is reached. The phases are separated, and the organic phase is washed with saturated brine and dried with magnesium sulfate (MgSO4) for 30 minutes.Finally, the solvent was removed under reduced pressure. Yield: 99% with a melting point of 105°C. 1 H NMR (500 MHz, DMSO) δ [ppm]: 6.44 (d, J = 3.1 Hz, 1H), 6.26 (d, J = 3.1 Hz, 1H), 5.02 (s, 2H), 4.37 (s, 2H), 2.56 – 2.44 (m, 4H). 13 C NMR (126 MHz, DMSO) δ [ppm]: 173.80, 172.34, 156.68, 148.83, 111.99, 108.25, 58.32, 56.10, 29.04. FTIR: ^ [cm -1 ] = 3460 (vsym OH), 3130 (vsym =CHR), 2929 (vasym -CH2-), 2867 (vsym -CH2-), 1704 (v sym C=O), 1558 (v sym C=C), 1170 (v sym COC) ESI-MS (m / z) = 251 [M+Na], 479 [2M+Na] Alternative reaction procedure using Pd / C-mediated hydrogenation: 1 gram of 4-((5-formylfuran-2-yl)methoxy)-4-oxobutanoic acid (4.4 mmol) is dissolved in 20 milliliters of ethanol, and 111 milligrams of palladium on carbon (Pd / C) is added as a catalyst. The solution is purged with hydrogen gas for 7 hours. Yield: 80% 1H NMR (500 MHz, DMSO) δ [ppm]: 6.44 (d, J = 3.1 Hz, 1H), 6.26 (d, J = 3.1 Hz, 1H), 5.02 (s, 2H), 4.37 (s, 2H), 2.56–2.44 (m, 4H). B) Polymerization: Method 1: The precursor substance is dissolved in DMSO or Cyrene. 1 mol% of methanesulfonic acid, HCl, H2SO4, formic acid (99%), or 1 wt% of a heterogeneous acid catalyst (Dowex, Amb 15, Amb 16, TiSi, zeolite) is added. The mixture is heated in a distillation apparatus at 150 °C and 30 mbar with continuous stirring. A black polymer is obtained. Method 2: The precursor substance is heated in a distillation apparatus for 5 h at 140 °C and 30 mbar. A black polymer is obtained. Method 3: The precursor substance is heated in a distillation apparatus for 5 h at 60 °C and 30 mbar. A black polymer is obtained. Glass transition temperature = -68 °C Melting temperature = 180 °C Decomposition temperature (5%) = 152 °C FTIR (PEE): ^ [cm -1] = 3500 -3300 (v -OH- residue alcohol, 3203 (v(-C=C-) furan), 2929 (v - (CH2)-), 1709 (v C=O, ester), 1682 (v C=O, residue acid), 1556 (d(C=C) furan), 1408 (d - (CH2)-), 1147 (v COC, ester). Characteristic broad band between 3500 - 2000 cm -1 (Hydrogen bonds, acid) Method 4: 1 g of the precursor substance (4.4 mmol) was dissolved together with 10% (w / w) immobilized lipase B from Candida antarctica (iCALB) and 10% (w / w) anhydrous CaCl2 in 5 ml of diethyl ether and evaporated at 40°C for 120 hours on a rotary evaporator. The solid was removed by filtration, and the solvent was evaporated under reduced pressure. A black, highly viscous oil was obtained. 1H NMR (500 MHz, DMSO) δ [ppm]: 6.51 (s), 5.01 (s), 2.54 (s). Alternative methods for various applications: Polymer synthesis by melt polycondensation. The precursor substance is heated to temperatures above 105°C until melted. The melt solidifies within 1 hour, depending on the initial temperature and synthesis pressure. Polymer synthesis by solution polymerization. The precursor substance is dissolved in MTHF and 10 mol% sulfuric acid is added as a catalyst. The mixture is heated under reflux for 6 hours, resulting in a black solution. After evaporation of the solvent under reduced pressure, a black, plasticine-like polymer is obtained. Polymer preparation for DMA analysis. The precursor substance is melted at 105°C and poured into a silicone mold, yielding a test specimen with dimensions of 5 mm:17 mm:3 mm (width:length:thickness). The mold is placed in a desiccator at 0.1 mbar.After 1, 3, and 5 hours at 140°C, the test specimens are removed from the mold and stored at room temperature. Polymer preparation for tensile strength analysis. The precursor substance is melted at 105°C and poured into a silicone mold, resulting in a test specimen with the dimensions of standardized tensile bars according to ISO 6922. The mold is placed in a desiccator at 0.1 mbar. After 3 hours at 140°C, the test specimens are removed from the mold and stored at room temperature. Polymer preparation for adhesion tests. The precursor substance is melted at 105°C, and the temperature is then raised to 140°C at a pressure of 0.1 mbar for one hour. A plasticine-like polymer mass is obtained. Alternatively, the precursor substance can be melted at 105°C. The temperature is lowered to 80°C for 3 hours. A plasticine-like mass is obtained that is suitable for solid adhesive applications. Sample preparation for adhesion tests.Plastic tensile bars with dimensions according to ISO 6922 are cut in half. Approximately 100 mg of the solid adhesive is applied to an area of ​​approximately 14 mm x 10 mm of the bar surface, and the halves are bonded together. For plastic, the adhesive is cured at 70°C for one hour. For wood and metal, the adhesive is cured at 90°C for 30 minutes. Patex and UHU general-purpose adhesives are applied to the surface of the test specimens that have been bonded together. The total curing time until performance testing is 2 days. The hot-melt adhesive is applied using a hot-melt glue gun. Molar mass distribution. Enzymatically produced: M. n = 726 g / mol (n=3); M w = 832 g / mol; Q (M w / M n ) = 1.15, T g = not determined Tensile test specimens: Mn = 24000 g / mol (n=106); Mw = 68300; Q (Mw / Mn) = 2.75, Tg = 50°C, Tm = 180°C, Tz = 230°C (succinic acid), T z= 450°C (succinic anhydride, by self-condensation of succinic acid) Adhesive: M n = 3400 g / mol (n=15); M w = 3513; Q (M w / M n ) = 1.03, T g = 10°C, curing times 1h at 70°C, or 30min at 90°C. Results of adhesion analyses of polymers of structure (VII) for bioadhesives, UHU superglue, PATTEX superglue, and hot melt adhesives to plastic, wood, and metal [N / mm 2] (VII) UHU PATTEX hot melt adhesive PP 0.69 ±0.15 0.12 ±0.05 0.23 ±0.10 0.59 ±0.01 ABS 2.80 ±0.01 0.31 ±0.01 0.74 ±0.00 0.49 ±0.01 PS 2.85 ±0.03 0.64 ±0.00 3.41 ±0.02 1.54 ±0.01 PMMA 1.90 ±0.01 0.85 ±0.01 3.18 ±0.01 0.97 ±0.01 PA66 2.83 ±0.02 0.97 ±0.01 4.43 ±0.01 0.83 ±0.01 PVC 0.46 ±0.09 0.13 ±0.06 1.79 ±0.37 0.46 ±0.03 PTFE 0.12 ±0.02 0.015 ±0.00 0.27 ±0.06 0.47 ±0.05 Wood 3.67 ±0.34 0.26 ±0.04 7.94 ±2.26 2.96 ±1.23 Copper 1.13 ±0.18 0.82 ±0.16 5.09 ±1.38 0.69 ±0.11 Bronze 1.34 ±0.01 0.14 ±0.08 6.99 ±3.28 0.98 ±0.26 Stainless steel 0.74 ±0.04 0.09 ±0.08 6.23 ±3.34 1.25 ±0.07 Cold rolled steel 3.26 ±1.85 0.24 ±0.20 8.12 ±2.08 0.81 ±0.21 Galvanized steel 0.79 ±0.03 0.02 ±0.01 4.34 ±1.16 0.90 ±0.15 Aluminum steel 0.52 ±0.08 0.08 ±0.06 5.73 ±1.40 0.85 ±0.22 Synthesis of the alternative precursor substance of structure (VIIIa) 20 g of succinic anhydride (0.2 mol) are heated to 60°C with 100 ml of ethanol and stirred for 16 hours. The excess ethanol is removed by vacuum distillation.The remaining colorless oil is dissolved in 100 ml of methyltetrahydrofuran (MTHF). Separately, 25.2 g of 5-hydroxymethyl-2-furfural (0.2 mol) is dissolved together with 55.44 ml of triethylamine (40.48 g, 0.4 mol) and 200 ml of MTHF and added dropwise while cooling. The mixture is stirred at room temperature for one hour and then at 60°C for another 3 hours. The mixture is filtered while cooled, and then 9.12 g of sodium borohydride (0.24 mol, 1.2 sodium equivalents) is added portionwise over 10 minutes. After the addition, the solution is stirred for another hour at room temperature. 5N HCl is added while cooling while stirring vigorously. The organic phase is separated and washed once with saturated NaCl solution, and the solvent is distilled off at 40°C and 250 mbar. The final product is a dark oil. Yield: 64%. Precursor: Aldehyde: 1H NMR (500 MHz, DMSO) δ [ppm]: 9.59 (s, 1H), 7.52 (d, J = 3.5 Hz, 1H), 6.79 (d, J = 3.7 Hz, 1H), 5.16 (d, J = 2.2 Hz, 2H), 4.06 – 4.01 (q, 2H), 2.81 – 2.45 (m, 4H), 1.15 (t, J = 7.2 Hz, 3H). 13 C NMR (126 MHz, DMSO) δ [ppm]: 178.94, 178.92, 178.43, 173.74, 172.56, 172.38, 172.24, 171.98, 155.87, 155.78, 152.90, 124.21, 113.39, 113.37, 110.15, 60.53, 58.19, 58.16, 58.12, 56.41, 36.53, 29.11, 29.01, 28.90, 14.47. ESI-MS (positive ion mode) m / z: 277 (M+Na) Alkohol: 1 H NMR (500 MHz, DMSO) δ [ppm]: 6.44 (d, J = 3.1 Hz, 1H), 6.27 (d, J = 3.1 Hz, 1H), 5.02 (s, 2H), 4.38 (t, J = 4.8 Hz, 2H), 4.05 (q, J = 7.4 Hz, 2H), 2.61 – 2.53 (m, 4H), 1.17 (t, J = 7.2, 5.5 Hz, 3H). FTIR: ^ [cm -1] = 3453, 2976, 2940, 2875, 1730, 1562, 1152, 1012 ESI-MS (positive ion mode) m / z: 279 (M+Na) Synthesis of the alternative precursor substance of structure (IXa) 10 ml of thionyl chloride is added dropwise to 10 g of fumaric acid monoethyl ester (69.4 mmol) and 50 ml of methyltetrahydrofuran (MTHF), and then stirred at 60°C for 16 h. Separately, 8.7 g of 5-hydroxymethyl-2-furfural (69 mmol) are dissolved with 20 ml of triethylamine (14.6 g, 144.3 mmol) in 100 ml of MTHF and added dropwise while cooled. The mixture is stirred for one hour at room temperature and then for a further 3 hours at 60°C. It is filtered and washed with saturated NaHCO3 solution and then with saturated NaCl solution. The solvent is distilled off at 40°C and 250 mbar. The final product is a dark oil. Yield: 45%. ESI-MS (positive ion mode) m / z: 275 (M+Na) FTIR: ^ [cm -1] = 3124, 2983, 2940, 2833, 1717, 1677, 1645, 1253, 1147, 1022 Synthesis of the alternative precursor substance of structure (IXb) Variant 1: 20 g of maleic anhydride (204 mmol) are heated together with 100 ml of ethanol at 60°C for 16 hours. The excess ethanol is removed by vacuum distillation. The colorless oil in the flask is dissolved in 100 ml of methyltetrahydrofuran (MTHF). Separately, 25.7 g of 5-hydroxymethyl-2-furfural (204 mmol) are dissolved together with 55.44 ml of triethylamine (40.48 g, 0.4 mol) and 200 ml of MTHF and added dropwise. The mixture is stirred for one hour at room temperature and then for another 3 hours at 60°C. The mixture is filtered and washed with saturated NaHCO3 solution and then with saturated NaCl solution. The solvent is distilled off at 40°C and 250 mbar. The final product is a dark oil. Yield: 55%. 1H NMR (500 MHz, DMSO) δ [ppm]: 9.61 (s, 1H), 7.53 (d, J = 3.5 Hz, 1H), 6.87 (d, J = 3.5 Hz, 1H), 5.33 (s, 2H), 4.20 (q, J = 7.1 Hz, 2H), 1.24 (t, J = 7.1 Hz, 3H). 13 C NMR (126 MHz, DMSO) δ [ppm]: 178.99, 178.97, 178.39, 164.75, 164.58, 164.25, 155.15, 153.01, 134.98, 134.63, 133.65, 132.70, 124.10, 113.77, 113.75, 110.12, 61.65, 61.61, 61.58, 61.54, 58.98, 58.94, 58.90, 56.41, 21.18, 14.51, 14.34, 14.32. FTIR: ^ [cm -1 ] = 3124, 2983, 2940, 2833, 1717, 1677, 1645, 1253, 1147, 1022 ESI-MS (positive ion mode) m / z: 275 (M+Na) Variant 2: 10 g of maleic anhydride (102 mmol) and 12.8 g of 5-hydroxymethyl-2-furfural (101.6 mmol) are dissolved in 50 ml of methyltetrahydrofuran (MTHF) and stirred for 16 h at 90°C. The solvent is distilled off at 40°C and 250 mbar. The final product is a dark solid. Yield: >98%. 1 H NMR (500 MHz, CDCl3) δ [ppm]: 9.64 (s, 1H), 7.26 (s, 1H), 6.69 (d, J = 3.6 Hz, 1H), 6.40 (d, J = 4.6 Hz, 2H), 5.30 (s, 2H). FTIR: ^ [cm-1 ] = 3123, 3056, 2985, 1728, 1706, 1677, 1645, 1156, 1023 ESI-MS (positive ion mode) m / z: 247 (M+Na) Synthesis of the alternative precursor substance of structure (XIIa) The precursor substance of structure (IXa) with Y=C2H4 is used with the transaminase R186 at a wet cell loading of 100 g / L. 1 mM pyridoxal phosphate (PLP) and 5 eq. L-alanine are added relative to the amount of the aldehyde component used. It is buffered with 50 mM potassium phosphate at pH = 7. 500 µL of the solution are heated to 40°C. Aldehyde concentration [mM] Product-related conversion after 24h [%] 10 100 50 81 100 20 200 12 1H NMR (500 MHz, CDCl3) δ [ppm]: 6.35 (d, J = 3.2 Hz, 1H), 6.13 (d, J = 3.2 Hz, 1H), 5.07 (s, 2H), 4.16 (q, J = 7.1 Hz, 2H), 3.84 (s, 2H), 2.66 (m, J = 10.1, 5.0 Hz, 4H), 1.28 (t, J = 6.9 Hz, 3H). Synthesis of polymer of structure (XI) with Y = C2H4. Synthesis of the precursor substance according to structure (XIV): 1.38 g of 5-(hydroxymethyl)furan-2-carbonitrile (11.2 mmol) and 1.13 g of succinic anhydride (11.3 mmol) are dissolved in 5 ml of MTHF and heated to boiling overnight. The solvent is evaporated at 60 °C and 250 mbar. A red-brown solid is obtained. Yield = 96%. 1 H NMR (500 MHz, CDCl3) δ 7.09 (d, J = 3.5 Hz, 1H), 6.55 (d, J = 3.6 Hz, 1H), 5.14 (s, 2H), 2.75 – 2.70 (m, 4H). FTIR (3): ^ [cm -1 ] = 3120 (v(-C=C-) furan), 1520 (d(C=C) furan), 2230 (v C#N, nitrile), 1730 (v C=O, ester), 1680 (v C=O, acid), 1160 (v COC, ester). Characteristic broad band between 3100 – 2300 cm -1(Hydrogen bonds, acid) Synthesis of polymer of structure (XVI) with Z = -(CH2)n- and W= -NH-(CH2)6-NH- or -NH-2,4-TDA-NH- or -NH-4,4'-MDA-NH- Step A) Synthesis of the precursor substance according to structure (XVII): Variant 1: 1 g of 5-HMF (7.9 mmol) is dissolved in 1 ml of water and 3.9 mmol of the diamine H2N-(CH2) n - NH2 is added at room temperature. Within one minute, compound (4) precipitates as a colorless solid and is filtered off. Yields: 60–86%. Variant 2: 1 g of 5-HMF (7.9 mmol) is melted at 40–70 °C, and 3.9 mmol of a diamine (n = 2, 4, 5, 6) is carefully added. Yield: > 99%. For n = 2 1 H NMR (500 MHz, DMSO) δ [ppm]: 8.11 (s, 1H), 6.82 (d, J = 3.3 Hz, 1H), 6.40 (d, J = 3.3 Hz, 1H), 5.39 (s, 1H), 4.42 (s, 2H), 3.77 (s, 2H). 13 C NMR (126 MHz, DMSO) δ [ppm]: 158.37, 151.15, 151.04, 115.86, 109.32, 61.72, 56.23. FTIR υ [cm -1 ]: 3300 cm -1 , 3100 cm -1 , 2950 cm -1 , 2850 cm-1 , 1646 cm -1 , 1525 cm -1 , 1022cm -1 ESI-MS positive ion mode m / z: 277.119 [C14H16N2O4H + ] Für n = 3 1 H NMR (500 MHz, DMSO) δ [ppm]: 8.12 (s, 2H), 6.82 (d, J = 3.3 Hz, 2H), 6.42 (d, J = 3.3 Hz, 2H), 5.38 (d, J = 7.0 Hz, 2H), 4.43 (d, J = 3.7 Hz, 4H), 3.55 (t, J = 6.9 Hz, 4H), 1.90 (p, J = 6.9 Hz, 2H). 13 C NMR (126 MHz, DMSO) δ [ppm]:158.29, 151.14, 150.37, 115.62, 109.29, 58.96, 56.24, 32.40. FTIR υ [cm -1 ]: 3300 cm -1 , 3100 cm -1 , 2950 cm -1 , 2850 cm -1 , 1646 cm -1 , 1525 cm -1 , 1022cm -1 ESI-MS positive ion mode m / z: 313.078 Für n = 4 1 H NMR (500 MHz, DMSO) δ [ppm]: 8.09 (s, 1H), 6.80 (d, 1H), 6.40 (d, J = 3.3 Hz, 1H), 3.50 (t, J = 6.2 Hz, 2H), 1.59 (p, 2H). 13 C NMR (126 MHz, DMSO) δ [ppm]: 158.22, 151.16, 149.92, 115.39, 109.25, 60.85, 56.23, 28.69. FTIR υ [cm -1 ]: 3300 cm -1 , 3100 cm-1 , 2950 cm -1 , 2850 cm -1 , 1646 cm -1 , 1525 cm -1 , 1022cm -1 ESI-MS positive ion mode m / z: 327.101 (C 16 H 20 N2O4Na + ) Für n = 5 1 H NMR (500 MHz, Acetone) δ [ppm]: 9.61 (s, 0H), 8.13 – 8.10 (m, 2H), 7.39 (d, J = 3.5 Hz, 1H), 6.76 (d, J = 3.4 Hz, 1H), 6.59 (d, J = 3.5 Hz, 1H), 6.40 (d, J = 3.3 Hz, 2H), 4.66 (s, 1H), 4.57 (s, 3H), 4.43 (s, 1H), 3.56 (td, J = 6.9, 1.4 Hz, 3H), 2.84 (s, 1H), 1.70 (p, J = 7.1 Hz, 3H), 1.49 – 1.40 (m, 2H). 13 C NMR (126 MHz, DMSO) δ [ppm]: 158.20, 151.17, 150.00, 115.39, 109.26, 61.09, 56.24, 30.80, 25.00. FTIR υ [cm -1 ]: 3300 cm -1 , 3100 cm -1 , 2930 cm -1 , 2860 cm -1 , 1646 cm -1 , 1525 cm -1 , 1020cm -1 ESI-MS positive ion mode m / z: 341.147 [C17H22N2O4Na + ] Für n = 6 1H NMR (500 MHz, acetone) δ [ppm]: 8.13 – 8.09 (m, 2H), 6.76 (d, J = 3.3 Hz, 2H), 6.40 (d, J = 3.3 Hz, 2H), 4.57 (s, 4H), 3.55 (td, J = 6.9, 1.4 Hz, 4H), 3.17 (t, J = 7.0 Hz, 1H), 1.67 (s, 4H), 1.57 (s, 2H), 1.46 – 1.37 (m, 3H). 13 C NMR (126 MHz, DMSO) δ [ppm]: 158.19, 151.18, 149.94, 115.37, 109.26, 61.14, 56.24, 30.96, 27.06. FTIR υ [cm -1 ]: 3300 cm -1 , 3100 cm -1 , 2930 cm -1 , 2860 cm -1 , 1658 cm -1 , 1525 cm -1 , 1020cm -1 ESI-MS positive ion mode m / z: 355.163 [C18H24N2O4Na + Variant 3: General procedure for the synthesis of aromatic precursors. 1 g of 5-HMF (4.4 mmol) is melted at 40°C, and 0.5 molar equivalents of the primary aromatic diamine are added using an Eppendorf pipette. The mixture is heated to 140°C until a viscous liquid forms. The mixture is then diluted with 2,4-TDA. 1H NMR (500 MHz, DMSO) δ [ppm]: 8.48 (s, 1H), 8.35 (s, 1H), 7.24 (d, J = 8.0 Hz, 1H), 7.09 (d, J = 3.3 Hz, 1H), 6.52 (dd, J = 13.1, 7.9, 3.4 Hz, 2H), 4.55 – 4.48 (m, 4H), 2.29 (s, 3H). 13 C NMR (126 MHz, DMSO) δ [ppm]: 159.70, 159.56, 151.72, 151.66, 151.62, 150.31, 148.75, 148.02, 131.23, 129.96, 118.50, 110.39, 109.98, 109.92, 109.05, 56.36, 17.81. FTIR υ [cm -1 ]: 3250 cm -1 , 3120 cm -1 , 3024cm -1 , 2940 cm -1 , 2860 cm -1 , 1620 cm -1 , 1573 cm -1 , 1530 cm -1 , 1485 cm -1 , 1015 cm -1 , 876cm -1 ESI-MS positive ion mode m / z: 361.064 (C 19 H 18 N2O4Na + ) Mit 4,4‘-MDA 1 H NMR (500 MHz, DMSO) δ [ppm]: 8.38 (s, 1H), 7.27 (d, J = 8.0 Hz, 2H), 7.19 (d, J = 8.1 Hz, 2H), 7.05 (d, J = 3.4 Hz, 1H), 6.51 (d, J = 3.5 Hz, 1H), 5.44 (t, J = 5.9 Hz, 1H), 4.48 (d, J = 6.0 Hz, 2H), 3.95 (s, 1H). 13C NMR (126 MHz, DMSO) δ [ppm]: 159.55, 151.68, 149.57, 147.98, 139.72, 129.98, 129.73, 129.61, 121.55, 121.37, 118.54, 109.89, 56.34. FTIR υ [cm -1 ]: 3275 cm -1 , 3126 cm -1 , 3020 cm -1 , 2930 cm -1 , 2840 cm -1 , 1620 cm -1 , 1614 cm- 1 , 1507 cm -1 , 1496 cm -1 , 1010 cm -1 , 959 cm -1 , 871 cm -1 , 800 cm -1 ESI-MS positive ion mode m / z: 415.124 (C 25 H 22 N2O4H + ) Thermal processes of the precursor substances according to structure (XVII) [°C] n= 2 3 4 5 6 2,4-TDA 4,4'-MDA T m 163 127 163 68 130 124 - Tb - - - 144 - - - T d 238 262 250 256 270 284 288 d - - - -40 - 8 32 d m : Melting point, T b : Boiling point, T d : Decomposition temperature, T g: Glass transition temperature determined by DSC analysis in the range from -50°C to 300°C under an N2 atmosphere with a heating / cooling rate of 20°C / min. Step B) Polymerization Variant 1: Conversion of the isolated precursor substance 0.5 g of the precursor substance according to structure (XVII) is dissolved in DMSO in a snap-cap vial. 0.9 eq of hexamethylene diisocyanate (HDI) is added volumetrically at room temperature. 0.01 mol% formic acid (99%) is added as a catalyst. Reaction time approx. 2 h. The solvent is removed from the resulting gel at 0.001 mbar and 50°C. Variant 2: One-pot synthesis 1 g of 5-HMF (7.9 mmol) is melted at 50°C and 3.9 mmol of the diamine H2N-(CH2)n-NH2 is carefully added. After a reaction time of 20 minutes, 0.95 eq. of hexamethylene diisocyanate is carefully added and the mixture is stirred for approximately 5 minutes until a black, highly viscous mass remains.Variant 3: Optimized conversion of the isolated precursor substance. 1 g of the precursor substance according to structure (XVII) was dissolved in 20 ml of DMSO at 40°C, and 1 molar equivalent of hexamethylene diisocyanate was added using an Eppendorf pipette to initiate the polymerization reaction. After 2 hours, the viscous solution was poured into a vessel containing 100 ml of DI water to precipitate the solid polymer. For n = 2, the glass transition temperature was 32 °C, the melting temperature was 159 °C, and the decomposition temperature (5%) was 148 °C. 1 H NMR (500 MHz, DMSO) δ [ppm]: 8.13 (s, 1H), 7.27 (s, 1H), 6.84 (s, 1H), 6.57 (s, 1H), 4.97 (s, 2H), 3.78 (s, 2H), 2.95 (d, J = 8.4 Hz, 2H), 1.35 (s, 2H), 1.21 (s, 2H). FTIR υ [cm -1 ]: 3312 cm -1 , 3127 cm -1 , 3060 cm -1 , 2936 cm -1 , 2857 cm -1 , 1700 cm -1 , 1645 cm- 1 , 1531 cm -1 , 1436 cm -1 , 1249 cm -1 , 1130 cm -1 , 1022 cm -1 For n = 31 H NMR (500 MHz, DMSO) δ [ppm]: 8.14 (s, 1H), 7.28 (s, 1H), 6.85 (s, 1H), 6.58 (s, 1H), 4.99 (s, 2H), 3.55 (t, J = 6.7 Hz, 2H), 2.96 (s, 2H), 1.93 – 1.87 (m, 1H), 1.36 (s, 3H), 1.22 (s, 3H). FTIR υ [cm -1 ]: 3306 cm -1 , 3133 cm -1 , 3060 cm -1 , 2936 cm -1 , 2857 cm -1 , 1682 cm -1 , 1644 cm- 1 , 1537 cm -1 , 1451 cm -1 , 1255 cm -1 , 1130 cm -1 , 1022 cm -1 Für n = 4 Glasübergangstemperatur: - Schmelztemperatur: 170 °C Zersetzungstemperatur (5%): 237 °C 1 H NMR (500 MHz, DMSO) δ [ppm]: 8.12 (d, J = 6.1 Hz, 1H), 7.26 (s, 1H), 6.84 (s, 1H), 6.58 (s, 1H), 4.98 (d, J = 4.6 Hz, 2H), 3.53 (s, 2H), 2.96 (s, 3H), 1.60 (s, 2H), 1.36 (s, 2H), 1.22 (s, 2H). FTIR υ [cm -1 ]: 3305 cm -1 , 3133 cm -1 , 3060 cm -1 , 2936 cm -1 , 2857 cm -1 , 1683 cm -1 , 1645 cm- 1 , 1538 cm -1, 1254 cm -1 , 1130 cm -1 , 1015 cm -1 Für n = 5 Glasübergangstemperatur: 55 °C Schmelztemperatur: 160 °C Zersetzungstemperatur (5%): 175 °C 1 H NMR (500 MHz, DMSO) δ [ppm]: 8.10 (s, 1H), 7.26 (s, 1H), 6.82 (s, 1H), 6.57 (s, 1H), 4.98 (s, 2H), 3.49 (s, 2H), 2.96 (d, J = 7.9 Hz, 2H), 1.60 (s, 2H), 1.36 (s, 4H), 1.21 (s, 2H). FTIR (5): ν [cm-1] = 3279 (v OH, Rest Alkohol),3080 (v(-C=C-) Furan),2906 & 2830 (v - CH2-) 1527 (d(C=C) Furan), 1730 (v C=O, Ester),1624 (v C=O, Amid), 1435 (d - CH2-), 1239 (v COC, Esther). Für n = 6 Glasübergangstemperatur: 50 °C Schmelztemperatur: - Zersetzungstemperatur (5%): 193 °C 1 H NMR (500 MHz, DMSO) δ [ppm]: 8.10 (s, 1H), 7.25 (d, J = 19.1 Hz, 1H), 6.83 (s, 1H), 6.59 (d, J = 17.6 Hz, 1H), 4.98 (s, 2H), 3.49 (d, J = 7.1 Hz, 2H), 3.07 – 2.77 (m, 2H), 1.57 (s, 2H), 1.43 – 0.96 (m, 7H). FTIR υ [cm -1 ]: 3305 cm -1 , 3133 cm -1 , 3060 cm -1 , 2936 cm -1 , 2857 cm-1 , 1686 cm -1 , 1651 cm- 1 , 1538 cm -1 , 1256 cm -1 , 1130 cm -1 , 1015 cm -1 For 2, 4-TDA FTIR υ [cm -1 ]: 3318 cm -1 , 3160 cm -1 , 3060 cm -1 , 3011 cm -1 , 2936 cm -1 , 2850 cm -1 , 1696 cm- 1 , 1625 cm -1 , 1537 cm -1 , 1241 cm -1 , 1128 cm -1 , 1015 cm -1 , 949 cm -1 , 879 cm -1 For 4,4'-MDA: FTIR υ [cm -1 ]: 3335 cm -1 , 3120 cm -1 , 3025 cm -1 , 2936 cm -1 , 2850 cm -1 , 1698 cm -1 , 1625 cm- 1 , 1498 cm -1 , 1241 cm -1 , 1128 cm -1 , 1015 cm -1 , 959 cm -1 , 798 cm -1 Thermal properties and molecular weight distribution of the polymer of structure (XVI) n= 2 3 4 5 6 2,4-TDA 4,4'-MDA Tg[°C] 30 41 - 56 49 30 80 T m [°C] - - 170 160 - - - Td 5%160 118 237 175 194 105 120 Td 30% 290 270 400 350 425 260 290 M n 3661 3573 8377 7203 7794 3427 2925 [g / mol] M w5526 6308 8681 14529 12369 4701 7528 [g / mol] Mn / Mw 1.5 1.8 1.1 2.0 1.6 1.4 2.6 The particular combinations of the components and features of the embodiments already mentioned are exemplary; the exchange and substitution of these teachings with other teachings contained in this document and the cited documents is also expressly contemplated. Those skilled in the art will recognize that variations, modifications and other embodiments described herein may also occur without departing from the spirit and scope of the invention. Accordingly, the above description is to be considered exemplary and not limiting. The word "comprising" as used in the claims does not exclude other components or steps. The indefinite article "a" does not exclude the meaning of a plural.The mere fact that certain dimensions are recited in mutually different claims does not indicate that a combination of those dimensions cannot be used to advantage. The scope of the invention is defined by the following claims and their equivalents.

Claims

Claims 1. Polymer comprising the structure in the repeating unit, where X is selected from a) -C(=NH)-O- b) -CH2-OC(=O)-YC(=O)-O- c) -CH2-OC(=O)-YC(=O)-NH- d) with Y being each independently selected substituted or unsubstituted C2 to C6 alkylene, alkenylene and alkynylene, where the substituents are selected from hydroxyl and aryl Z being each independently selected substituted or unsubstituted C2 to C6 alkylene, alkenylene and alkynylene, phenylene, Ph-(CH2)k-Ph (with k=2, 4, 5 and 6), furan where the substituents are selected from hydroxyl, aryl and C1 to C6 alkylene W is selected from Z and -NH-Z-NH- .

2. A polymer according to claim 1, comprising at least one section in which the structure (I) forms the repeating unit.

3. A polymer according to any one of claims 1 to 2, comprising the structure:

4. Polymer according to claim 3, wherein n is from ≥10 to ≤2,500.

5. Polymer according to one of claims 1 to 4 having an average molecular weight of ≥ 3,000 Da to ≤ 1,000,000 Da.

6. Polymer according to one of claims 1 to 5, wherein Y is selected from C2 to C4 alkylene.

7. Polymer according to one of claims 1 to 6, wherein Z is each independently selected from substituted or unsubstituted C2 to C6 alkylene, alkenylene and alkynylene, phenylene, Ph-(CH2)k-Ph (with k=2, 4, 5 and 6), furan, wherein the substituents are selected from hydroxyl and aryl.

8. Polymer according to one of claims 1 to 7, wherein Z is selected from Y selected from C2 to C6 alkylene 9. Polymer according to one of claims 1 to 8, wherein Z is selected from substituted or unsubstituted phenyl.

10. Polymer according to any one of claims 1 to 9, wherein Z is selected from substituted or unsubstituted Ph-(CH2) k-Ph (with k=2, 4, 5, and 6).

11. Use of a polymer according to any one of claims 1 to 10 for one or more of the following applications: - Composite materials - Materials for pipes or profiles - Foams - Bioadhesives / adhesives - Textile materials - Coating materials, in particular lacquers - Light scavenger in the solar industry - Materials for printing ink or graphic applications - Packaging material 12. Connections of the structure: where R 1 is selected from CH2OH, CH2NH2, C(=N-OR 3 )H, CHO and CN R 2 is selected from -CH2-OC(=O)-YC(=O)-OR 3 , -CH2-OC(=O)-YC(=O)-NH2, with R 3 = H or C1 to C6 alkyl.

13. Compounds according to claim 12, wherein R 1 is selected from CH2OH, CH2NH2, C(=N-OR 3 )H and CN.

Images