Furan-containing polymers

Abstract

The present invention relates to furan-containing polymers, as well as precursors for the production of these furan-containing polymers and production processes for both the polymers and the precursors.

Description

[0001] 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.

[0002] 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.

[0003] In particular, polymers containing furan are being considered, as 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 obtained by isomerization from the readily available and inexpensive sugar D-glucose.

[0004] However, there is still a need for furan-containing polymers and processes for producing them, and the task for the person skilled in the art is to provide further polymers, precursors therefor and processes for producing these substances.

[0005] This object is achieved by a polymer according to claim 1. Accordingly, a polymer is provided comprising the structure (I) in the repeating unit, wherein X is selected from a) -C(=NH)-O- b) -CH2-OC(=O)-YC(=O)-O- c) -CH2-OC(=O)-YC(=O)-NH- d) e) with Y is each independently selected substituted or unsubstituted C1 to C6 alkylene, alkenylene and alkynylene, wherein 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 (with k=1 to 6) and furan, wherein the substituents are selected from hydroxyl and aryl; and W is selected from Z and -NH-Z-NH-

[0006] It has been found that these novel polymers have outstanding properties that appear to be suitable for a wide range of applications.

[0007] The present invention therefore 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, especially varnishes. - “light scavenger” in the solar industry - Materials for printing ink or graphic applications - Packaging material

[0008] Preferably, Y is selected from C2 to C4 alkylene.

[0009] Preferably, Z is selected from C2 to C6 alkylene.

[0010] The present invention also relates to compounds of the following structure:wherein R 1 is selected from CH2OH, CH2NH2, C(=N-OR 3 )H and CN R 2 is selected from -CH2-OC(=O)-YC(=O)-OR 3 , -CH2-OC(=O)-YC(=O)-NH2, and with R 3 = H or C1 to C6 linear, branched or cyclic alkyl.

[0011] These compounds can serve as precursor materials for the preparation of the polymers according to the invention.

[0012] In the context of the present invention, the structural unit refers to and / or comprises in particular a single chemical bond to another structural unit within the same molecule.

[0013] Within the present application, the abbreviations (= Y, Z, R n etc.) always have the same chemical structures unless otherwise stated.

[0014] According to a preferred embodiment of the invention, the polymer comprises at least one section in which the structure (I) forms the repeating unit.

[0015] According to a preferred embodiment, the polymer consists of repeating units of structure (I), ie it has the following structure (III):wherein 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.

[0016] According to a preferred embodiment, the polymer of 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.

[0017] Preferred embodiments of the invention are discussed below:

[0018] According to a preferred embodiment of the invention, there is provided a polymer comprising the structure (IV) in the repeating unit:

[0019] According to a preferred embodiment of the invention, the polymer comprises at least one section in which the structure (IV) forms the repeating unit.

[0020] According to a preferred embodiment, the polymer consists of repeating units of structure (IV), ie it has the following structure (V):wherein 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.

[0021] 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.

[0022] The present invention further comprises a process for preparing a polymer of structure (V) comprising the 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.

[0023] 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

[0024] 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 ≤ 200°C

[0025] 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, especially varnishes. - “light scavenger” in the solar industry - Materials for printing ink or graphic applications - Packaging material

[0026] According to a preferred embodiment of the invention, there is provided a polymer comprising the structure (VI) in the repeating unit:

[0027] According to a preferred embodiment of the invention, the polymer comprises at least one section in which the structure (VI) forms the repeating unit.

[0028] According to a preferred embodiment, the polymer consists of repeating units of structure (VI), ie it has the following structure (VII):wherein 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.

[0029] 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, 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.

[0030] 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, especially varnishes. - “light scavenger” in the solar industry - Materials for printing ink or graphic applications - Packaging material

[0031] 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 such a polymer with excellent properties, in particular with regard to the glass transition temperature, the molecular weight and / or the melting temperature, can be prepared.

[0032] 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% (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 preferably used here. Lipase B from Candida antarctica in immobilized form is particularly suitable for the production of polyamides and polyesters.

[0033] According to a preferred embodiment of the invention, a process for preparing 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).

[0034] According to a preferred embodiment of the invention, there is provided a polymer comprising the structure (X) in the repeating unit:

[0035] According to a preferred embodiment of the invention, the polymer comprises at least one section in which the structure (X) forms the repeating unit.

[0036] According to a preferred embodiment, the polymer consists of repeating units of structure (X), ie it has the following structure (XI):wherein 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.

[0037] According to a preferred embodiment, the polymer consists of structure (XI) 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.

[0038] 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, especially varnishes. - “light scavenger” in the solar industry - Materials for printing ink or graphic applications - Packaging material

[0039] 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.

[0040] Surprisingly, it was found that such a polymer with excellent properties, particularly with regard to the glass transition temperature, molecular weight and / or melting temperature, can be produced.

[0041] The compounds of structure (XII) can be prepared in a simple manner by reduction of the corresponding compounds of structure (XIII): which in turn are accessible from 5-(hydroxymethyl)furan-2-carbonitrile.

[0042] Alternatively, the compounds of structure (XII) can be prepared in a simple manner by reduction of the corresponding compounds of structure (XIV); these in turn are accessible from 5-(hydroxymethyl)furfural, e.g.: via structure (IX).

[0043] 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.

[0044] Thus, according to a preferred embodiment of the present invention, a process for preparing the polymer having structure (XI) comprises the following steps: a) conversion of 5-(hydroxymethyl)furfural to a compound of structure (IX); b) Optionally, conversion of the compound of structure (IX) to a compound of structure (XIII) or (XIV) c) reductive amination or reduction to obtain a compound of structure (XII); d) Polymerization

[0045] According to a preferred embodiment of the invention, there is provided a polymer comprising the structure (XV) in the repeating unit:

[0046] According to a preferred embodiment of the invention, the polymer comprises at least one section in which the structure (XV) forms the repeating unit.

[0047] According to a preferred embodiment, the polymer consists of repeating units of structure (XV), ie it has the following structure (XVI):wherein 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.

[0048] 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.

[0049] 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, especially foams - Materials for pipes or profiles, packaging - Foams - Bioadhesives - Textile materials - Coating materials, especially varnishes. - “light scavenger” in the solar industry - Materials for printing ink or graphic applications - Packaging material

[0050] The present invention also relates to a production process for producing polymers of structure (XVI), comprising the reaction of a precursor substance of 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 4 selected from H or C1 to C6 alkyl

[0051] It has been found that suitable polymers can be produced in this way.

[0052] The compounds of structure (XVII) can in turn be obtained by reacting 5-hydroxymethylfurfural with H2N-Z-NH2.

[0053] According to a preferred embodiment of the invention, there is provided a polymer comprising the structure (XVIII) in the repeating unit:

[0054] According to a preferred embodiment of the invention, the polymer comprises at least one section in which the structure (XVIII) forms the repeating unit.

[0055] 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.

[0056] According to a preferred embodiment, the polymer consists of 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.

[0057] According to a preferred embodiment of the invention, the use of a polymer according to 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, especially varnishes. - “light scavenger” in the solar industry - Materials for printing ink or graphic applications - Packaging material

[0058] 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

[0059] It has been found that suitable polymers can be produced in this way.

[0060] The compounds of structure (XX) can in turn be obtained by reduction of the compounds of structure (XVII).

[0061] The aforementioned 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 in terms of their size, shape, material selection and technical conception, so that the selection criteria known in the field of application can be applied without restriction.

[0062] Further details, features and advantages of the subject matter of the invention emerge from the dependent claims and from the following examples, which are purely illustrative and not to be regarded as limiting.

[0063] The description of syntheses known from the literature is omitted. Synthesis of polymethylfuranimidate (structure (V)):Synthesis 1:

[0064] 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)): v [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:

[0065] 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:

[0066] 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:

[0067] 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 of polymer of structure (VII) with Y = C2H6A) Synthesis of the precursor substance (structure (VIII) with Y = C2H6) Variant 1: One-pot synthesis

[0068] 5.58 g of 5-HMF (44.3 mmol) and 4.42 g of succinic anhydride (44.2 mmol) were dissolved in 5 mL of MTHF and refluxed overnight. The solution was cooled to 0°C in an ice bath, and 50 mL of MTHF was added. 2 g of NaBH4 (1.2 Na eq.) were added successively to the solution over 5 min, and the suspension was stirred overnight at room temperature. After removal of the solvent in vacuo, the colorless solid was dissolved in 50 mL of MQ water while cooling in an ice bath. The basic aqueous solution (pH = 9) was extracted twice with 20 mL of MTHF. After phase separation, the aqueous solution was acidified to pH < 4 using 1 M HCl and ice-bath cooling. A colorless solid precipitated. The solid was filtered through a fluted filter, and the aqueous phase was 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:

[0069] 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 in an ice bath. The suspension is stirred for a further 3 hours at room temperature, and the solvent is then removed at 250 mbar and 40 °C. While cooling in 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 to pH < 4 with 1 N HCl while cooling continuously in an ice bath. A colorless solid precipitates, which is washed with 20 ml of MTHF. The acidic aqueous solution is extracted once with 50 ml of MTHF. After phase separation, the organic phases are combined, dried over MgSO4 and reduced at 40°C and 150 mbar to obtain a colorless solid. Yield: 91%.

[0070] 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). B) Polymerization:Procedure 1:

[0071] The precursor substance is dissolved in DMSO or Cyrene. 1 mol% 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:

[0072] 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:

[0073] 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): v [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) Synthesis of polymer of structure (XI) with Y = C2H6Synthesis of the precursor substance according to structure (XIV):

[0074] 1.38 g of 5-(hydroxymethyl)furan-2-carbonitrile (11.2 mmol) and 1.13 g of succinic anhydride (11.3 mmol) were dissolved in 5 mL of MTHF and heated to boiling overnight. The solvent was evaporated at 60 °C and 250 mbar. A red-brown solid was obtained. Yield = 96%.

[0075] 1H 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).

[0076] FTIR (3): v [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 (XVII) with Z = -(CH2) n - and W= -NH-(CH2)6-NH-Step A) Synthesis of the precursor substance according to structure (XVII): Variant 1:

[0077] 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:

[0078] 1 g of 5-HMF (7.9 mmol) wird bei 70 °C geschmolzen and 3.9 mmol eines Diamins (n ​​= 2, 4, 5, 6) wird vorsichtig hinzugegeben. Ausbeauty: > 99 %. For n = 2 1 H NMR (500 MHz, DMSO) δ 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).s (3). For n = 5 1H NMR (500 MHz, Acetone) δ 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 (3), H = 9), J 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, 1. Hz (p 1. 3), 1.49 - 1.40 (m, 2H). For n = 6 1H NMR (500 MHz, Acetone) δ 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, 1, 4.9 (d) 3, 3.5). 4H), 3.17 (t, J = 7.0 Hz, 1H), 1.67 (s, 4H), 1.57 (s, 2H), 1.46 - 1.37 (m, 3H). Step B) PolymerizationVariant 1: Conversion of the isolated precursor substance

[0079] 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. The reaction time is approximately 2 h. The solvent is removed from the resulting gel at 0.001 mbar and 50 °C. Variant 2: One-pot synthesis

[0080] 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. For n = 2 Glass transition temperature: 32 °C Melting point: 159 °C Decomposition temperature (5%): 148°C For n = 4 Glass transition temperature: - Melting temperature: 170 °C Decomposition temperature (5%): 237°C For n = 5 Glass transition temperature: 55 °C Melting temperature: 160 °C Decomposition temperature (5%): 175°C FTIR (5): v [cm-1] = 3279 (v OH, remainder alcohol), 3080 (v (-C=C-) furan), 2906 & 2830 (v - CH2-) 1527 (d (C=C) furan), 1730 (v C=O, ester), 1624 (v C=O, amide), 1435 (d - CH2-), 1239 (v COC, esters). For n = 6 Glass transition temperature: 50 °C Melting point: - Decomposition temperature (5%): 193°C

[0081] The particular combinations of components and features of the aforementioned embodiments are exemplary; the replacement 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 measures are recited in mutually different claims does not indicate that a combination of those measures cannot be used to advantage.The scope of the invention is defined in the following claims and their equivalents.

Claims

[1] A polymer comprising the structure in the repeating unit, wherein X is selected from a) -C(=NH)-O- b) -CH2-OC(=O)-YC(=O)-O- c) -CH2-OC(=O)-YC(=O)-NH- d) e) with Y is each independently selected substituted or unsubstituted C2 to C6 alkylene, alkenylene and alkynylene, wherein the substituents are selected from hydroxyl Z is 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 W is selected from Z and -NH-Z-NH- [2] Polymer according to claim 1, comprising at least one section in which the structure (I) forms the repeating unit. [3] Polymer according to claim 1 or 2 having the structure [4] Polymer according to any one of claims 1 to 3, comprising the structure: [5] The polymer of claim 4, wherein n is from ≥10 to ≤2,500. [6] Polymer according to any one of claims 1 to 5 having an average molecular weight of ≥ 3,000 Da to ≤1,000,000 Da. [7] Polymer according to any one of claims 1 to 6, wherein Y is selected from C2 to C4 alkylene. [8] Polymer according to any one of claims 1 to 7, wherein Z is selected from Y is selected from C2 to C6 alkylene [9] Use of a polymer according to any one of claims 1 to 8 for one or more of the following applications: - Composite materials - Materials for pipes or profiles - Foams - Bioadhesives - Textile materials - Coating materials, especially varnishes. - “light scavenger” in the solar industry - Materials for printing ink or graphic applications - Packaging material [10] Compounds of the structure: where R 1 is selected from CH2OH, CH2NH2, C(=N-OR 3 )H and CN R 2 is selected from -CHz-OC(=O)-YC(=O)-OR 3 , -CH2-OC(=O)-YC(=O)-NH2,and with R 3 = H or C1 to C6 alkyl