Bisphenol a alternatives

Abstract

A compound of formula (I) wherein R1 is H, C1-C18-alkyl, C5-C10-aryl, or 3 to 8-membered hetaryl, which alkyl, aryl or hetaryl is unsubstituted or substituted with at least one substituent R5, R2 is independently C1-C18-alkyl or C2-C18-alkenyl, R3 is independently C1-C18-alkoxy, R4 is independently H or C1-C18-alkoxy, and R5 is independently halogen, hydroxyl, C1-C18-alkoxy, C3-C8-cycloalkyl, C3-C8-cycloalkoxy, 3 to 8- membered heterocycloalkyl, 3 to 8-membered heterocycloalkoxy, C5-C10-aryl, C5-C10-aryloxy, 3 to 8- membered hetaryl or 3 to 8-membered hetaryloxy, which alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy may be unsubstituted or substituted is a bisphenol A alternative. Polymers are obtained by reacting the compound of formula (I) with an activated carbonic acid derivative, by reacting the compound of formula (I) with a compound of formula (IV) being obtainable by reacting the compound of formula (I) with epichlorohydrin, or by reacting the compound of formula (IV) with a (poly)amine.

Description

[0001] Bisphenol A Alternatives

[0002] The present invention relates to bisphenol A alternatives, a method for preparing bisphenol A alternatives, a polymer comprising repeating units derived from bisphenol A alternatives, and a method for preparing said polymer.

[0003] Bisphenol A (BPA) is utilised ubiquitously as a co-monomer for polycarbonates, epoxy resins, high-performance plastics and resins, due to the excellent thermal and mechanical properties its materials possess. Typically, BPA is synthesised by the condensation of two phenols with one molecule of acetone:

[0004]

[0005] BPA production accounts for the majority of the global phenol demand, which phenol is typically fossil-derived. In order to reduce the demand for phenol and, simultaneously, reduce the demand of fossil resources, BPA-alternatives having comparable reactivity are of special interest.

[0006] For example, a BPA-alternative is described in S.-F. Koelewijn et al., Green Chem. 2017, 19, 2561-2570:

[0007]

[0008] Bisphenolic compound 5,5'-methylenebis(4-n-propylguaiacol) was synthesized by acid-catalysed condensation from 4-n-propylguaiacol.

[0009] L. Trullemans et al., Nature Sustainability 2023, 6, 1693-1704 describe a synthetic pathway towards bisguaiacols as genuinely sustainable Bisphenol A alternatives from a renewable lignin source:

[0010] OH

[0011] R

[0012]

[0013] = Me, COOH, COOMe, COOEt Preferably, the BPA-alternatives should be based on renewable resources. Lignin is a major waste product in cellulose-driven industries, e.g. paper & pulping, bulk chemicals, bioethanol etc. Lignin serves as a potential source of renewable, functionalised aromatics which may, e.g., replace phenol. Structurally, lignin is a highly heterogeneous and complex biopolymer matrix. Depolymerisation of typical industrial (technical) lignins gives access to monophenolics. Besides depolymerization, "lignin-first” technologies such as reductive catalytic fractionation (RCF) have provided an alternative way to access monophenolics. Propylated guaiacol and syringol are the mono- and di-methoxylated phenols, respectively, that are obtained as the primary products in relatively high quantities through such technologies.

[0014] It is therefore an object of the present invention to provide suitable renewable alternatives to bisphenol A.

[0015] Bisphenol A is known to possess strong endocrine disrupting ability as an estrogenic compound. With its pervasive use, the increased exposure to BPA provides heightened risk of adverse health effects due to it leaching from materials over time. It is desirable to tackle such chemical problems by molecular redesign, to come to both safe as well as sustainably produced alternatives.

[0016] It is therefore a further object of the present invention to provide suitable less toxic alternatives to bisphenol A, i.e. alternatives to bisphenol A having a reduced cytotoxicity.

[0017] The object(s) of the invention is solved by a compound of formula (I)

[0018]

[0019] (I)

[0020] wherein

[0021] Ri is H, Ci-C -alkyl, Cs-C -aryl, or 3 to 8-membered hetaryl,

[0022] which alkyl, aryl or hetaryl is unsubstituted or substituted with at least one substituent R5,

[0023] R2 is independently Ci-C -alkyl or C2-Ci8-alkenyl,

[0024] R3 is independently Ci-C -alkoxy,

[0025] R4 is independently H or C i-C -alkoxy, Rs is independently halogen, hydroxyl, Ci-C -alkoxy, C -Cs-cycloalkyl, C -Cs-cycloalkoxy, 3 to 8- membered heterocycloalkyl, 3 to 8-membered heterocycloalkoxy, Cs-C -aryl, Cs-C -aryloxy, 3 to 8- membered hetaryl or 3 to 8-membered hetary loxy,

[0026] which alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl or hetary loxy may be unsubstituted or substituted, and

[0027] a is an integer of from 0 to 5.

[0028] The compounds of the present invention provide a variety of advantages:

[0029] In the case of R4 being H, the compounds of the invention are bisguaiacols (BGs). In the case of R4 being alkoxy, the compounds of the invention are bissyringols (BSs). Both bisguaiacols and bissyringols are a promising, potentially safer, and more sustainable alternatives to bisphenol A. An alternative route to bifunctional alternatives of bisphenol A, i.e. bisphenol A having a bridgehead functionality, has surprisingly been found: A carboxylic group or derivative thereof is introduced on the bridgehead by a condensation reaction using a functional aldehyde, such as glyoxylic acid.

[0030] The functional group provides the opportunity to derivatise the monomer, by esterification to provide, e.g. ethyl or benzyl esters. Starting from the free carboxylic acid functional group, the inventive method provides compounds which may, after decarboxylation, also be a new pathway towards bis(guaiacol) formaldehyde(s).

[0031] These compounds having the carboxylic acid functional group allowed for synthesis of charged polymers such as charged polycarbonates. " Charged polymers” are polymers having multiple charged groups. Such polymers may also be referred to as polyanions. This allows, inter alia, for preparing polymers having desired solubility properties in aqueous media. The carboxylic acid functional group also allows for esterification of the resulting polymers. For example, polymers having at least one carboxylic acid functional group may be reacted with diols and / or polyols resulting in crosslinking. Typically, the so obtained crosslinked polymers are more rigid, compared to non-crosslinked polymers.

[0032] A pathway to obtain BGs and BSs as compounds of the present invention starts from lignin as renewable source. Therefore, bisguaiacols and bissyringols constitute attractive, bio-based alternatives for fossil-derived phenol being the most common starting material for bisphenol A, as outlined above.

[0033] The inventive compounds have proven advantageous for their estrogenic potency against 17β-oestradiol (E2) using an hERα reporter cell assay.

[0034] R2 may independently be a C2-C18-al k- 1 -en-1 -yl. In this case, the carbon-carbon double bond of R2 is conjugated with the aromatic ring of the compound of formula (I). In a preferred embodiment,

[0035] Ri is H, Ci-Ci2-alkyl, Cs-Cs-aryl or 3 to 7-membered hetaryl, more preferably H, Ci-Cs-alkyl, Cs-Ce-aryl or 3 to 6-membered hetaryl,

[0036] R2 is independently Ci-Ci2-alkyl or C2-Ci2-alkenyl, more preferably Ci-Cs-alkyl or C2-C3-alkenyl,

[0037] R3 is independently Ci-Ci2-alkoxy, more preferably Ci-Cs-alkoxy, and

[0038] R4 is independently H or C i-Ci2-alkoxy, more preferably H or Ci-Cs-alkoxy.

[0039] Preferably, a is 0. In this case, for example, the compound of formula (I) may be obtained by reacting excess amounts bisguaiacols and / or bissyringols with glyoxylic acid, as described in detail below. This results in a compound of formula (I) as follows:

[0040]

[0041] In an embodiment, R5 is alkoxy which alkoxy may be substituted with at least one substituent selected from C1-Cis-alkoxy and halogen, preferably Ci-Ci2-alkoxy and halogen, more preferably Ci-Cs-alkoxy and halogen.

[0042] In an embodiment, R5 is cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl or hetary loxy which cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy may be substituted with at least one substituent selected from Ci-Ci8-alkyl, Ci-Cis-alkoxy and halogen, preferably Ci-Ci2-alkyl, Ci-Ci2-alkoxy and halogen, more preferably Ci-Cs-alkyl, Ci-Cs-alkoxy and halogen.

[0043] Especially preferred are compounds of formula (I) in which

[0044] R1 is H, ethyl or benzyl,

[0045] R2 is methyl, ethyl or n-propyl,

[0046] R3 is methoxy,

[0047] R4 is H or methoxy, and

[0048] a is 0. The invention further relates to a method for preparing the compound of formula (I) as described above, comprising reacting a compound of formula (II)

[0049] OH

[0050] R2

[0051]

[0052] (II)

[0053] with a compound of formula (III)

[0054] O O

[0055]

[0056] (III)

[0057] and, optionally, in a case where Ri is H, converting the compound with Ri being H into a compound with Ri as defined above other than H,

[0058] to obtain the compound of formula (I).

[0059] In a preferred embodiment, a is 0 in the compound of formula (III). In this case, the compound of formula (III) is selected from glyoxylic acid and esters of glyoxylic acid (glyoxylates) such as ethyl glyoxylate or benzyl glyoxylate.

[0060] The method may be carried out in solution, i.e. using a solvent, or neat. Suitable solvents are selected from dichloromethane, dichloroethane, chloroform, ethyl acetate, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylformamide, N-methyl-2-pyrrolidone, and toluene. Carrying out the method neat is preferred.

[0061] The method may be carried out in the presence of a catalyst, in particular an acidic catalyst. Suitable catalysts are known to the skilled person. For example, p-toluene sulfonic acid may be used as catalyst.

[0062] In a case where Ri is H in the compound of formula (III) shown above, the reaction with the compound of formula (II) yields a compound in which Ri is H, i.e. a compound having a free carboxylic acid. In this case, the process may further comprise converting said compound with Ri being H into a compound with Ri as defined above other than H, i.e. into a compound with Ri being Ci-Ci8-alkyl, Cs-C -aryl, or 3 to 8-membered hetaryl, which alkyl, aryl or hetaryl is unsubstituted or substituted with at least one substituent Rs, preferably into a compound with Ri being ethyl or benzyl. In other words, the compound having a free carboxylic acid may be converted into an ester, e.g. with an alcohol such as ethanol or an alkyl halogenide such as benzyl bromide. Suitable reaction conditions for carrying out such reactions are known by the skilled person and typically involve catalysts, e.g. acidic catalysts such as sulfuric acid or basic catalysts such as K2CO3. In a preferred embodiment, the method comprises depolymerizing lignin to obtain the compound of formula (II). Lignin is one renewable resource that shows promise as a desirable alternative to petroleum feedstocks, largely due to its abundance as a byproduct of pulp and paper refining. This advantageous method allows for utilizing a compound of formula (II) obtained from the renewable resource lignin.

[0063] The invention further relates to a compound of formula (IV)

[0064]

[0065] wherein

[0066] Ri is H, Ci-C -alkyl, Cs-C -aryl, or 3 to 8-membered hetaryl,

[0067] which alkyl, aryl or hetaryl is unsubstituted or substituted with at least one substituent R5,

[0068] R2 is independently Ci-C -alkyl or C2-Ci8-alkenyl,

[0069] R3 is independently Ci-Cis-alkoxy,

[0070] R4 is independently H or C i-C -alkoxy,

[0071] R5 is independently halogen, hydroxyl, Ci-Cis-alkoxy, C -Cs-cycloalkyl, C -Cs-cycloalkoxy, 3 to 8- membered heterocycloalkyl, 3 to 8-membered heterocycloalkoxy, Cs-C -aryl, Cs-C -aryloxy, 3 to 8- membered hetaryl or 3 to 8-membered hetary loxy,

[0072] which alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl or hetary loxy may be unsubstituted or substituted, and

[0073] a is an integer of from 0 to 5.

[0074] Suitably, the compound of formula (IV) is obtained by reacting the compound of formula (I) with epichlorohydrin.

[0075] The invention further relates to a polymer being obtainable by reacting the compound of formula (I) with the compound of formula (IV).

[0076] The invention further relates to a polymer being obtainable by reacting the compound of formula (IV) with a curing agent such as an amine-based curing agent and / or a phenol-based curing agent. Amine-based curing agents comprise (poly)amines, i.e. monoamines and / or polyamines. Phenol-based curing agents comprise diphenols and / or polyphenols. Suitable a (poly)amines are selected from

[0077] - aliphatic monoamines such as linear or branched aliphatic C2-Ci8-monoamines such as ethylamine, propylamine, butylamine, pentylamine, hexylamine, isohexylamine, 2-ethylhexylamine, octylamine, tertoctylamine, dodecylamine, stearylamine etc.; cycloaliphatic monoamines such as cyclopentylamine, cyclohexylamine etc.; unsaturated aliphatic monoamines such as oleylamine etc.; and aromatic monoamines such as aromatic Ce-Cis-monoamines such as such as aniline, p-toluidine, and naphthyl amine etc.,

[0078] - aliphatic diamines or polyamines such as ethylene diamine, 1,2-propane diamine, 1,3-propane diamine, 1,4- butane diamine, 1,3-pentane diamine, 1,5-pentane diamine, 1,6-hexane diamine, 1,8-octane diamine, neopentane diamine, 1,10-decane diamine, 1,12-dodecane diamine, 2-methylpentane-1,5-diamine, N, N'- dimethyl-ethylene diamine, diethylene triamine, dipropylene triamine, triethylene tetraamine, tetraethylene pentamine, pentaethylene hexamine, 2,2-dimethylpropylenediamine, trimethylhexamethylenediamine, 1-(3- aminopropyl)-3-aminopropane, 1,3-bis(3-aminopropyl)propane, 4-ethyl-4-methylamino-1 -octylamine, N, N, N-tris-(2-aminoethyl)-amine, N, N, N'-tris-(2-aminoethyl)-ethylene diamine, polyethylene imines, polyvinylamines, polyallylamines, polylysines, iminobis-propylamine, N-(2-aminoethyl)-1,3-propane diamine, tetrapropylene pentamine, tripropylene tetramine, N, N-bis-(6-aminohexyl)-amine, N, N'-bis-(3- aminopropyl)-ethylene diamine, aminoethylethanolamine,

[0079] - cycloalkylenediamines or (cyclo)alkylenepolyamines such as cyclohexyldiamines such as 1,2- diaminocyclohexane, 1-methyl-2,4-diaminocyclohexane, 1-methyl-2,6-diaminocyclohexane, 1-amino-3- aminomethyl-3,5,5-trimethylcyclohexane (isophorone diamine), bis-(4-aminocyclohexyl)-methane, bis-(4- amino-3-methylcyclohexyl)-methane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 2,5-bisaminomethyl tetrahydrofuran, 4,4'-diamino-dicyclohexylmethane, 3,3’-dimethyl-4,4'-diamino-dicyclohexylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, N- cyclohexylpropylene-1,3-diamine, 4,8-diamino-tricyclo[5.2.1.0]decane, norbornandiamine, menthanediamine, menthenediamine, Baxxodur EC210 (BASF SE), 3-((3-(((2-cyanoethyl)amino)methyl)- 3,5,5-trimethylcyclohexyl)amino)propiononitrile,

[0080] - heterocyclic diamines or polyamines such as piperazine, 2,5-dimethyl piperazine, N-(2-piperazinoethyl) ethylene diamine, N, N'-bis-(2-aminoethyl)-piperazine, N-[N-(2-aminoethyl)-2-amino-ethyl]-N'-(2- aminoethyl)-piperazine, N-(2-aminoethyl)-N'-(2-piperazinoethyl)-ethylene diamine, N, N-bis-(2-aminoethyl)- N-(2-piperazinoethyl)-amine, N, N-bis-(2-piperazinoethyl)-amine,

[0081] - hydrazine, aminoacid hydrazides, hydrazides of semicarbazido carboxylic acids, bis-hydrazides, bis- semicarbazides,

[0082] - guanidine,

[0083] - aromatic diamines or polyamines such as melamine, 3,3'-diaminobenzidine, 2,4,6-triaminopyrimidine, 2,4- bis-(4'-aminobenzyl)-aniline, diethyl-toluene diamine isomers, toluene diamine isomers, xylylene diamine isomers, 1,2-phenylene diamine, 1,3-phenylene diamine, 1,4-phenylene diamine, methylene-bis- (phenylamine) isomers such as 4,4'-diamino-diphenylmethane or 4,4'-diaminodiphenylsulfone, 2,5- bisaminomethyl furan, 1,5-naphthalene diamine, aniline, alkyl anilines, toluidine, t-butyl-toluene diamine isomers, methylene-bis-(o-dichloroaniline) (MOCA), 2,4-diaminoalkylbenzene isomers having 8 to 15 carbon atoms in the alkyl chain, and

[0084] - polyetheramines (alkylene diamines or alkylene polyamines comprising ether groups) such as difunctional and trifunctional primary polyetheramines based on polypropylene glycol, polyethylene glycol, polybutylene oxide, poly-(1,4-butanediol), polytetrahydrofuran (poly-THF) or polypentylene oxide, e.g. 4,7,10- trioxatridecan-1,3-diamine, 4,7, 10-trioxatridecan-1, 13-diamine, 1,8-diamino-3,6-dioxaoctane (XTJ-504, Huntsman), 1,10-diamino-4,7-dioxadecane (XTJ-590, Huntsman), 1,12-diamino-4,9-dioxadodecane (BASF SE), 1,3-diamino-4,7,10-trioxatridecane (BASF SE), primary polyetheramines based on polypropylene glycol with an average molecular weight of 230, such as Polyetheramine D 230 (BASF SE) or Jeffamine® D 230 (Huntsman), difunctional, primary polyetheramines based on polypropylene glycol with an average molecular weight of 400, e.g. Polyetheramine D 400 (BASF SE) or Jeffamine® XTJ 582 (Huntsman), difunctional, primary polyetheramines based on polypropylene glycol with an average molecular weight of 2000, e.g. Polyetheramine D 2000 (BASF SE) or Jeffamine® XTJ 582 (Huntsman), difunctional, primary polyetheramines based on polypropylene glycol with an average molecular weight of 2000, e.g. Polyetheramine D 2000 (BASF SE) or Jeffamine® XTJ 582 (Huntsman), e.g. Polyetheramine D 2000 (BASF SE), Jeffamine® D2000 or Jeffamine® XTJ 578 (both from Huntsman), difunctional, primary polyetheramines based on propylene oxide with an average molecular weight of 4000, e.g. Polyetheramine D 4000 (BASF SE), trifunctional, primary polyetheramines prepared by reaction of propylene oxide with trimethylolpropane, followed by amination of the terminal OH groups with an average molecular weight of 403, e.g. Polyetheramine T 403 (BASF SE) or Jeffamine® T 403 (Huntsman), trifunctional, primary polyetheramines prepared by reaction of propylene oxide with glycerol, followed by amination of the terminal OH groups with an average molecular weight of 5000 (Huntsman), trifunctional, primary polyetheramine prepared by reaction of propylene oxide with glycerol, followed by amination of the terminal OH groups with an average molecular weight of 5000, such as Polyetheramine T 5000 (BASF SE) or Jeffamine® T 5000 (Huntsman), aliphatic polyetheramines, which are composed of a polyethylene glycol grafted with propylene oxide and have an average molecular weight of 600, such as Jeffamine® ED-600 or Jeffamine® XTJ-501 (Huntsman), aliphatic polyetheramines which are composed of a polyethylene glycol grafted with propylene oxide and have an average molecular weight of 900, such as Jeffamine® ED-900 (Huntsman), aliphatic polyetheramines which are composed of a polyethylene glycol grafted with propylene oxide and have an average molecular weight of 2000, e.g. Jeffamine® ED-2003 (Huntsman), difunctional, primary polyether amines produced by amination of a diethylene glycol grafted with propylene oxide with an average molecular weight of 220, e.g. Jeffamine® HK-511 (Huntsman), aliphatic polyether amines based on a copolymer of poly (tetramethylene ether glycol) and polypropylene glycol with an average molecular weight of 1000 (Huntsman), aliphatic polyether amines based on a copolymer of poly(tetramethylene ether glycol) and polypropylene glycol with an average molecular weight of 1000, such as Jeffamine® XTJ-542 (Huntsman), aliphatic polyether amines based on a copolymer of poly(tetramethylene ether glycol) and polypropylene glycol with an average molecular weight of 1900, such as Jeffamine® XTJ-542 (Huntsman), aliphatic polyether amines based on a copolymer of poly(tetramethylene ether glycol) and polypropylene glycol with an average molecular weight of 1900, such as Jeffamine® XTJ-542 (Huntsman), polyether triamines based on an at least trivalent alcohol grafted with butylene oxide with an average molecular weight of 400, e.g. Jeffamine® XTJ-566 (Huntsman), aliphatic polyether amines produced by amination of alcohols grafted with butylene oxide with an average molecular weight of 219, e.g. Jeffamine® XTJ-568 (Huntsman), polyetheramines based on pentaerythritol and propylene oxide with an average molecular weight of 600, e.g. Jeffamine® XTJ-616 (Huntsman), polyetheramines based on triethylene glycol with an average molecular weight of 148, e.g. Jeffamine® EDR-148 (Huntsman), difunctional, primary polyether amines produced by amination of an ethylene glycol grafted with propylene oxide with an average molecular weight of 176, e.g. Jeffamine® EDR-176 (Huntsman) and polyether amines prepared by amination of polytetrahydrofuran (Poly-THF) with an average molecular weight of 250, e.g. PolyTHF-Amin 350 (BASF SE).

[0085] For example, the diphenol may include monomeric or oligomeric diphenols, bisphenols, and mixtures thereof, which bears at least one unsubstituted phenyl carbon atom at a 2-, 4-, or 6-phenolic ring position. In an embodiment, the diphenols may include any substituted or unsubstituted diphenol which bears at least one unsubstituted phenyl carbon atom at a 2-, 4-, or 6-phenolic ring position such as, hydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, biphenol, thiodiphenol, and a difunctional phenolic hardener such as D. E. H.

[0086] 80 phenolic resin (an oligomer derived from bisphenol A and bisphenol A diglycidyl ether).

[0087] The polyphenol may include any substituted or unsubstituted polyphenol or mixtures thereof which bears at least one unsubstituted phenyl carbon atom at a 2-, 4-, or 6-phenolic ring position. The polyphenol may have a novolac structure. A phenol novolac resin, a triazine skeleton containing phenol novolac resin, a naphthol novolac resin, a naphthol aralkyl type resin, a triazine skeleton-containing naphthol resin, and a biphenyl aralkyl type phenol resin are preferable. In an embodiment, polyphenols may include any substituted or unsubstituted polyphenol which bears at least one unsubstituted phenyl carbon atom at a 2-, 4-, or 6-phenolic ring position such as tris(4-hydroxyphenyl)ethane, dicyclopentadiene-phenol adducts (for example SD-1806 DCPD-phenol adduct available from Momentive, Inc.), phenol novolac resins (for example, Rezicure 3000 phenol novolac resin available from SCI), cresol novolac resins (for example SD-1612 o-cresol novolac resin available from Momentive, Inc.), and bisphenol A novolac resins (for example SD-1502 bis A-formaldehyde resin available from Momentive, Inc.). A commercially available biphenyl aralkyl type phenol resin may be " MEH-7700”, " MEH-7810”, " MEH-7851”, and " MEH7851-4H” (available from Meiwa Plastic Industries, Ltd.) and " GPH” (available from NIPPON KAYAKU Co., Ltd.), a commercially available naphthol novolac resin may be " NHN” and " CBN” (available from NIPPON KAYAKU Co., Ltd.), a commercially available naphthol aralkyl type resin may be " SN170”, " SN180”, " SN190”, " SN475”, " SN485”, " SN495”, " SN395”, and " SN375” (available from Tohto Kasel Co., Ltd.), a commercially available phenol novolac resin may be " TD2090” (available from DIG Corporation), and a commercially available triazine skeleton-containing phenol novolac resin may be " LA3018”, " LA7052”, " LA 7054”, and " LA1356” (available from DIG Corporation). Hence, the invention further relates to polymer comprising repeating units of formula (V)

[0088] R2

[0089]

[0090] wherein

[0091] Ri is H, Ci-Ci8-alkyl, Cs-Cio-aryl or 3 to 8-membered hetaryl,

[0092] which alkyl, aryl or hetaryl is unsubstituted or substituted with at least one substituent R5,

[0093] R2 is independently Ci-C -alkyl or C2-Ci8-alkenyl,

[0094] R3 is independently Ci-Cis-alkoxy,

[0095] R4 is independently H or C i-C -alkoxy,

[0096] R5 is independently halogen, hydroxyl, Ci-Cis-alkoxy, C -Cs-cycloalkyl, C -Cs-cycloalkoxy, 3 to 8- membered heterocycloalkyl, 3 to 8-membered heterocycloalkoxy, Cs-C -aryl, Cs-Cio-aryloxy, 3 to 8- membered hetaryl or 3 to 8-membered hetary loxy,

[0097] which alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl or hetary loxy may be unsubstituted or substituted,

[0098] a is an integer of from 0 to 5, and

[0099] OH OH O I I

[0100] X

[0101]

[0102] is (X-1)—C—, (X-2)

[0103] wherein

[0104] Y is a residue of a (poly)amine having n amino groups, and

[0105] n is an integer of from 1 to 8, preferably 1 to 3.

[0106] A "residue of a (poly)amine having n amino groups” is a (poly)amine having n amino groups from which all primary amino groups are removed.

[0107] The invention further relates to a method for preparing the polymer as described above, comprising reacting the compound of formula (I) with an activated carbonic acid derivative to obtain the polymer comprising repeating units of formula (V) with X being (X-1). This method yields polycarbonates.

[0108] The activated carbonic acid derivative may be selected from carbonyl dichloride (phosgene), carbonyl dibromide (bromophosgene), bis(trichloromethyl) carbonate (triphosgene), N, N'-carbonyldiimidazole, dimethyl carbonate, diethyl carbonate, and diphenyl carbonate. The invention further relates to a method for preparing the polymer as described above, comprising reacting the compound of formula (I) with the compound of formula (IV) to obtain the polymer comprising repeating units of formula (V) with X being (X-2). This method yields epoxy resins.

[0109] The invention further relates to a method for preparing the polymer as described above, comprising reacting the compound of formula (IV) with a (poly)amine, i.e. a monoamine or a polyamine to obtain the polymer comprising repeating units of formula (V) with X being (X-3). This method yields epoxy resins.

[0110] Fig. 1 depicts estradiol (ER) activity after 24 h expressed as the response compared to the maximum response observed with 17β-oestradiol (E2), with DMSO as the negative control.

[0111] The present invention is further illustrated by the figure, and examples that follow.

[0112] Examples

[0113] Chemicals

[0114] Technical grade ethanol, ethyl acetate, acetone, dichloromethane (DCM) and toluene were obtained from VWR Chemicals. Sodium hydroxide (99>%) was also obtained from VWR Chemicals. Pyridine (99>%), potassium carbonate (98%) and stabilised allyl bromide (99%) were obtained from Acros Organics. Deuterated chloroform (D, 99.8%) was provided by Buchem. 2-methoxy-4-propylphenol (>99%) and Silica gel 60 (230-400 mesh) were obtained from Sigma Aldrich. Glyoxylic acid monohydrate (98%), benzyl bromide (98%), was obtained from Fisher Scientific.

[0115] Equipment

[0116] ATR-FTIR spectra were recorded on a PerkinElmer Frontier FTIR spectrometer equipped with a PerkinElmer Universal ATR Sampling Accessory with a diamond / ZnSe plate and a LiTaO3mid-IR detector.

[0117] NMR spectra were acquired at 298 K on either a Varian VNMRS 400 with a PFG probe, or an Agilent MRF400 spectrometer equipped with a OneNMR probe and Optima Tune system at 400 MHz. NMR samples were measured in standard 5 mm-OD NMR tubes and chemical shifts (5) are reported in ppm. Acquired NMR data was analysed and processed using Mestrenova (version 14.2.0-26256). Standard1H sequences were used with 8 scans.13C spectra were acquired with a standard pulse sequence and inverse gated1H decoupler mode, with 256 scans. 241155WC01 12

[0118] GPC measurements were performed on a modular Shimadzu system comprising an SCI-40 controller module, DGU-203 degassing unit, SIL-40 autosampler, CTO-40C column oven, and RID-20A refractive index detector. Separation was performed across an Agilent Technologies PLgel 5µm Guard 50 x 7.5 mm guard column followed by two Agilent Technologies PLgel 5µm MIXED-D 300 x 7.7 mm columns in series.

[0119] MDSC measurements were performed using a TA Instruments Trios DSC and the data was analysed within the TA instruments Trios software (v5.7.1.74).

[0120] TGA measurements were carried out with a TA Instruments TGA Q50 Thermographic Analyzer. The resulting data was analysed using TA instruments Universal Analysis 2000.

[0121] Methods

[0122] Gel Permeation Chromatography (GPC)

[0123] Polymer samples were dissolved in DMF (1 mg mL-1) and filtered with a 45 µm PTFE syringe filter before GPC analysis. The sample injection volume was 10 µL and samples were run with a flow rate of 1 mL min-1at 65 °C. Molecular weight determinations were based on calibrations with polystyrene standards (Mn= 4, 7, 13, 20, 50, 100, 200, 300 kg mol-1).

[0124] Thermogravimetric Analysis (TGA)

[0125] Approximately 2 to 10 mg of sample was weighed into a platinum pan, which was then loaded into the sample chamber. The entire measurement was performed under a nitrogen atmosphere. For data acquisition, the sample was heated from room temperature (approx. 22 °C) to 600 °C at 20°C min-1.

[0126] Modulated Differential Scanning Calorimetry (MDSC)

[0127] Approximately 2 to 5 mg Polymer sample was weighed into a Tzero low-mass aluminium pan, fitted with a Tzero lid. Once the pan was loaded into the DSC cell, the sample was equilibrated to 25 °C. The entire measurement was performed under a nitrogen atmosphere. Two heating cycles were then performed. For the first cycle, the sample was heated to 105 °C at 10 °C min-1, held isothermal for 20 min, cooled to -50 °C at 10 °C min-1and held isothermal for 1 min to anneal the sample, remove any residual solvents and to erase the sample's thermal history. Data was acquired on the second heating cycle, whereby the temperature was ramped from -50 °C to 130 °C at 3 °C min-1with a sinusoidal temperature modulation of 0.66 °C per 50 s. Each sample was measured in duplicate, and the average value for Tgwas taken. Nuclear Receptor Activity Assays

[0128] Reporter genes assays were employed to assess nuclear receptor activity of the bisguaiacols on the estrogen receptor, with VM7Luc4E2 cells. Detailed procedures are reported in, e.g. D. Bozdag et al., Dysregulation of Adipogenesis and Disrupted Lipid Metabolism by the Antidepressants Citalopram and Sertraline, Toxicol. Appl. Pharmacol. 2024, 486, 116937. All experiments included full concentration response curves of estradiol (ER), to ensure the proper performance of the assays. DMSO was used a solvent for all chemicals and did not exceed 0.1% in the assay media. Luminescence and Fluorescence were measured on a Tecan plate reader (Infinite M plex). Estrogen receptor activity (EA) was investigated using an hERo assay. This was benchmarked against bisphenol A with 17β-oestradiol (E2) and DMSO as a positive and negative control, respectively. The VM7luc42E2 cell line was utilised, and the EA was measured by luciferase activity after 24 h with fluorescent measurements. ER activity was measured at non-cytotoxic concentrations, to a maximum of 10 µM of bisaryl compounds.

[0129] Syntheses

[0130] Reference compound

[0131] OH OH

[0132]

[0133] m,m'-bis(4-propylguaiacol)formaldehyde (BGF)

[0134] Formaldehyde (1.33 mL, 37 % w / w in H2O, 18 mmol), 4-propylguaiacol (6.0 g, 36 mmol) and HCl (2.5 M, 50 mL) were stirred at 1000 rpm for 6 h at 100 °C. The solution was allowed to cool and the aqueous phase was decanted. The solution was dissolved in Et20 (10 mL), dried over MgSO4, filtered, and crystallised from hot Et2O with slow addition of heptane.

[0135] 1H NMR (400 MHz, CDCl3): δ 6.67 (s, 2H), 6.47 (s, 2H), 5.33 (s, 2H), 3.87 (s, 6H), 2.59 - 2.35 (m, 4H), 1.64 -1.49 (m, 4H), 0.96 (d, J = 7.3 Hz, 6H). Inventive compounds (according to formula (I))

[0136]

[0137] m,m’-bis(4-propylguaiacol)glyoxylic acid (BGG)

[0138] 4-Propylguaiacol (3.32 g, 20 mmol) was dissolved in 2-methyl tetrahydrofuran (16 mL) in a round bottom flask, after which a solution of glyoxylic acid monohydrate (1.629 g, 22 mmol) and p-toluene sulfonic acid (30 mg, 174 µmol) in distilled H2O (1.3 mL) was added dropwise. The reaction mixture was heated to 110 °C for 4 h. The reaction mixture was reduced in vacuo, redissolved in DCM (5 mL) and washed with distilled H2O (3x 5 mL). The organic phase was dried over MgSO4, filtered, and reduced in vacuo to give yellow oil which slowly crystallised to an off-white solid. The crude product was purified by recrystallising from DCM, yielding white crystals (60% isolated yield).

[0139] 1H NMR (400 MHz, CDCl3): δ 6.73 (s, 2H), 6.67 (s, 2H), 5.43 (br s, 1H), 5.26 (s, 1H), 3.86 (d, J = 0.5 Hz, 6H), 2.55 - 2.38 (m, 4H), 1.66 - 1.46 (m, 4H), 0.95 (t, J = 7.3 Hz, 6H).

[0140] 13C NMR (101 MHz, CDCl3): δ 178.79, 145.78, 143.63, 132.76, 128.50, 115.31, 112.26, 56.02, 48.79, 34.95, 24.41, 14.27.

[0141] OH OH

[0142]

[0143] m,m’-bis(4-propylguaiacol)glyoxylic acid ethyl ester (BGG-Et)

[0144] BGG (1 g, 2.57 mmol) was dissolved in EtOH (25 mL) and concentrated H2SO4(>95 %, 0.4 mL) was added. The reaction mixture was heated to reflux for 3 days. Then, the mixture was allowed to cool, the solvent was removed in vacuo, and 10 mL of H2O was added, followed by EtOAc (5 mL). The mixture was then transferred to a separatory funnel and the aqueous phase was extracted twice more with EtOAc. The combined organic phases were then dried over Na2SO4, filtered, reduced in vacuo. The crude was then purified by column chromatography over silica (EtOAC: pentane, 1:1) and the purified product was isolated as an orange amorphous solid (861 mg, 80% yield).

[0145] 1H NMR (400 MHz, CDCl3): δ 6.69 (s, 2H), 6.66 (s, 2H), 5.40 (br s, 2H), 5.22 (s, 1H), 4.25 - 4.13 (m, 2H), 3.86 (s, 6H), 2.53 - 2.34 (m, 4H), 1.63 - 1.42 (m, 4H), 1.24 (t, J = 7.0, 3H), 1.01 - 0.90 (t, J = 7.3, 6H).13C NMR (101 MHz, CDCl3): δ 173.63, 145.55, 143.58, 132.55, 129.33, 115.33, 112.16, 61.22, 56.01, 49.17, 34.95, 24.39, 14.32, 14.30.

[0146]

[0147] m,m’-bis(4-propylguaiacol)glyoxylic acid benzyl ester (BGG-Bn)

[0148] To a stirred solution of BGG (0.300 g, 772 µmol) in dimethylformamide (1.5 mL) was added K2CO3(107 mg, 772 µmol). The mixture was stirred for 10 min at room temperature, after which benzyl bromide (132 mg, 0.92 mL, 772 µmol) was added dropwise. The reaction mixture was stirred at 35 °C for 16 h, after which it was removed from the heat. The mixture was then diluted in 15 mL Et2O, and 5 mL of H2O was added. The mixture was transferred to a separatory funnel and the layers were separated. The aqueous layer was washed with Et20 (3 x 15 mL) and the combined organic phases were back extracted with distilled H2O (5 x 5 mL). The organic phase was then dried over MgSO4, filtered, and reduced in vacuo to yield a yellow / orange oil. The crude product was purified by column chromatography over silica (EtOAC: pentane, 1:1) and the purified product was isolated as a yellow oil (220 mg, 59% yield).

[0149] 1H NMR (400 MHz, CDCl3): δ 7.39 - 7.27 (m, 5H), 6.67 (s, 2H), 6.65 (s, 2H), 5.34 (s, 2H), 5.25 (s, 1H), 5.17 (s, 2H), 3.86 (d, J = 0.5 Hz, 6H), 2.47 - 2.29 (m, 5H), 1.54 - 1.36 (m, 3H), 0.88 (t, J = 7.3 Hz, 6H).

[0150] 13C NMR (101 MHz, CDCl3): δ 145.61, 143.61, 132.55, 129.14, 128.54, 128.21, 115.38, 112.16, 66.93, 56.03, 49.16, 34.94, 24.35, 14.27.

[0151] Abbreviations in Fig. 1

[0152] In Fig. 1, the following abbreviations were used:

[0153] - urn Micrometer

[0154] - DMSO Dimethylsulfoxide

[0155] - BGF m,m'-Bis(4-propylguaiacol)formaldehyde

[0156] - BGG-Acid m,m’-Bis(4-propylguaiacol)glyoxylic acid

[0157] - BGG-Et m,m’-Bis(4-propylguaiacol)glyoxylic acid ethyl ester

[0158] - BGG-Bn m,m’-Bis(4-propylguaiacol)glyoxylic acid benzyl ester

[0159] - BPA Bisphenol A

[0160] - E2 17p-Oestradiol Nuclear Receptor Activity Assays

[0161] Results of the nuclear receptor activity assay experiments are shown in Fig. 1.

[0162] Fig. 1 depicts estradiol (ER) activity after 24 h expressed as the response compared to the maximum response observed with 17β-oestradiol (E2), with DMSO as the negative control.

[0163] As can be seen from the results in Fig. 1, bisphenol A showed affinity to the oestrogen receptor at 1 and 10 µM, in line with literature. Some slight EA could be seen for BGF, BGG, BGG-Et and BGG-Bn at the concentrations tested, but in all cases the effect was much lower than for BPA. Interestingly, BGG-Bn showed a slightly elevated EA (although still far lower than that of BPA) when compared to that of BGG or BGF, which may be a result of lowering the polarity of the bridgehead position.

[0164] Polymerization (general procedure)

[0165] 257.43 µmol of the bisguaiacol compound to be polymerized (BGF, BGG, BGG-Et, BGG-Bn) was dissolved in a sodium hydroxide solution (25.7 mg, 643.57 µmol, 0.4 mL H2O) under stirring and placed in an oil bath at 35 °C, forming a dark orange solution upon total dissolution. The stirring rate was then increased to approx. 1000 rpm. Separately, triphosgene (38.2 mg, 128.7 µmol) was dissolved in DCM (0.6 mL) and added dropwise to the strongly stirring solution. The reaction was left to stir for 15 minutes, after which it was removed from heating and stirring. 0.5 mL of H2O was added to assist in separating the layers and the aqueous layer was decanted with a pipette. The organic phase was washed with water (2 x 0.5 mL), and then added dropwise to ice-cold methanol under strongly stirring. An immediate precipitate formed, and after 5 minutes of stirring, the same was removed. The supernatant was removed by decantation, or in some cases, filtration, to yield an off-white to orange solid as the product.

[0166] Reference polymer

[0167] Poly(m,m'-bis(4-propylguaiacol)formaldehyde) (pBGF)

[0168] 1H NMR (400 MHz, TFA-d1): δ 6.93 (br s, 2H), 6.73 (br s, 2H), 3.98 - 3.78 (m, 8H), 2.53 (br s, 4H), 1.55 (br s, 4H), 0.90 (br s, 6H).

[0169] The peak at 3.98 - 3.78 ppm corresponds to both methoxy groups and the methylene protons which are observed as overlapping signals. Inventive polymers

[0170] The following inventive polymers pBGG (from BGG), pBGG-Et (from BGG-Et) and pBGG-Bn (from BGG-Bn) were prepared:

[0171]

[0172] The polymer properties of the obtained reference polymer pBGF and the inventive polymers pBGG, pBGG-Et and pBGG-Bn are shown in the following and Table 1.

[0173] Poly (m,m'-bis(4-propylguaiacol)glyoxylic acid) (pBGG)

[0174] 1H NMR (400 MHz, TFA-d1): δ 7.57 - 6.26 (m, 2H), 6.05 - 4.93 (m, 1H), 3.92 (br s, 6H), 3.14 - 2.09 (m, 4H), 1.59 (br s, 4H), 1.29 - 0.60 (m, 6H).

[0175] Poly (m,m'-bis(4-propylguaiacol)glyoxylic acid ethyl ester) (pBGG-Et)

[0176] 1H NMR (400 MHz, TFA-d1): δ 6.94 (s, 2H), 6.87 (s, 2H), 5.48 (s, 1H), 4.32 (m, 2H), 3.95 - 3.81 (m, 6H), 2.51 (br s, 4H), 1.56 (m, 4H), 1.25 (m, 3H), 0.92 (m, 6H).

[0177] Poly (m,m’-bis(4-propylguaiacol)glyoxylic acid benzyl ester) (pBGG-Bn)

[0178] 1H NMR (400 MHz, TFA-d1): δ 7.22 (br s, 5H), 6.94 (br s, 2H), 6.75 (br s, 2H), 4.06 - 3.62 (m, 6H), 2.44 (s, 4H), 1.51 (s, 4H), 0.87 (s, 6H). Table 1. Polymer properties of pBGF, pBGG, pBGG-Et and pBGG-Bn.

[0179] Mn[1] Mw[2] Đ [2] Td,io% I3’4’ Td.max I3’5’ V] [kg / mol] [kg / mol] [°C] [°C] [°C] pBGF* 5377 6114 1.14 324 370 73

[0180] pBGG 2243 2249 1.00 2177 [7] 307 49

[0181] pBGG-Et 7336 9155 1.25 341 369 64

[0182] pBGG-Bn 4869 5380 1.10 305 361 100

[0183]

[0184] 1] Determined by GPC

[0185] [2] Polydispersity

[0186] [3] Determined by TGA

[0187] [4] Td,io% = decomposition temperatures, defined by a 10% weight loss; determined by TGA

[0188] [5] Td.max = temperature of the largest maximum in the derivative weight loss curve

[0189] [6] Tg= glass transition temperature; determined by DSC

[0190] [7] Residual solvent in the sample led to a lower value than the true value.

[0191] * reference polymer

[0192] It can be seen from the results shown in Table 1 that for all tested monomers according to the invention (BGG, BGG-Et and BGG-Bn), polymers were obtained. BGG-Bn has a very high Tgof 100 °C indicating that the bulk of the bridgehead position has a large influence on material properties. Polymers having high glass transition temperatures Tgare beneficial for thermally stressed material components.

Claims

Claims1. A compound of formula (I)(I)whereinRi is H, Ci-Ci8-alkyl, Cs-C -aryl, or 3 to 8-membered hetaryl,which alkyl, aryl or hetaryl is unsubstituted or substituted with at least one substituent Rs, R2 is independently Ci-Ci8-alkyl or C2-C -alkenyl,R3 is independently Ci-Cis-alkoxy,R4 is independently H or Ci-Cis-alkoxy, andRs is independently halogen, hydroxyl, Ci-Cis-alkoxy, C -Cs-cycloalkyl, C -Cs-cycloalkoxy, 3 to 8- membered heterocycloalkyl, 3 to 8-membered heterocycloalkoxy, Cs-Cw-aryl, Cs-Cw-aryloxy, 3 to 8-membered hetaryl or 3 to 8-membered hetaryloxy,which alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy may be unsubstituted or substituted.

2. The compound of claim 1, wherein R2 is independently a C2-C -alk-1 -en-1 -yl.

3. The compound of claim 1 or 2, whereinR1 is H, Ci-Ci2-alkyl, Cs-Cs-aryl or 3 to 7-membered hetaryl, preferably H, Ci-Cs-alkyl, Cs-Ce-aryl or 3 to 6-membered hetaryl,R2 is independently Ci-Ci2-alkyl or C2-Ci2-alkenyl, preferably Ci-Cs-alkyl or C2-C3-alkenyl, R3 is independently Ci-Ci2-alkoxy, preferably Ci-Cs-alkoxy, andR4 is independently H or C i-Ci2-alkoxy, preferably H or Ci-Cs-alkoxy.

4. The compound of any one of the preceding claims, whereinthe alkoxy of Rs is substituted with at least one substituent selected from C 1-C -al koxy and halogen, preferably Ci-Ci2-alkoxy and halogen, more preferably Ci-Cs-alkoxy and halogen, andthe cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy of Rs is substituted with at least one substituent selected from Ci-Ci8-alkyl, Ci-C -alkoxy and halogen, preferably Ci-Ci2-alkyl, Ci-Ci2-alkoxy and halogen, more preferably Ci-Cs-alkyl, Ci-Cs-alkoxy and halogen.

5. The compound of any one of the preceding claims, whereinRi is H, ethyl or benzyl,R2 is methyl, ethyl or n-propyl,R3 is methoxy, andR4 is H or methoxy.

6. A method for preparing the compound of formula (I) of claim 1, comprising reacting a compound of formula (II)OHR2(II)with a compound of formula (III)R-O^YHo(III)and, optionally, in a case where R1 is H, converting the compound with R1 being H into a compound with R1 as defined in claim 1 other than H,to obtain the compound of formula (I).

7. The method of claim 6, comprising depolymerizing lignin to obtain the compound of formula (II).

8. A compound of formula (IV)(IV)whereinR1 is H, Ci-Ci8-alkyl, Cs-Cio-aryl or 3 to 8-membered hetaryl,which alkyl, aryl or hetaryl is unsubstituted or substituted with at least one substituent R5, R2 is independently C1-C18-alkyl or C2-C18-alkenyl,R3 is independently C1-C18-alkoxy,R4 is independently H or C1-C18-alkoxy, andR5 is independently halogen, hydroxyl, C1-C18-alkoxy, C3-C8-cycloalkyl, C3-C8-cycloalkoxy, 3 to 8- membered heterocycloalkyl, 3 to 8-membered heterocycloalkoxy, C5-C10-aryl, C5-C10-aryloxy, 3 to 8-membered hetaryl or 3 to 8-membered hetaryloxy,which alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy may be unsubstituted or substituted.

9. A polymer comprising repeating units of formula (V)whereinR1 is H, C1-C18-alkyl, C5-C10-aryl or 3 to 8-membered hetaryl,which alkyl, aryl or hetaryl is unsubstituted or substituted with at least one substituent R5, R2 is independently C1-C18-alkyl or C2-C18-alkenyl,R3 is independently C1-C18-alkoxy,R4 is independently H or C1-C18-alkoxy,R5 is independently halogen, hydroxyl, C1-C18-alkoxy, C3-C8-cycloalkyl, C3-C8-cycloalkoxy, 3 to 8- membered heterocycloalkyl, 3 to 8-membered heterocycloalkoxy, C5-C10-aryl, C5-C10-aryloxy, 3 to 8-membered hetaryl or 3 to 8-membered hetaryloxy,which alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy may be unsubstituted or substituted, andOH OHwhereinY is a residue of a (poly)amine having n amino groups, andn is an integer of from 1 to 8, preferably 1 to 3.

10. A method for preparing the polymer of claim 9, comprisingreacting the compound of formula (I) of claim 1 with an activated carbonic acid derivative to obtain the polymer comprising repeating units of formula (V) with X being (X-1),reacting the compound of formula (I) with the compound of formula (IV) of claim 8 to obtain the polymer comprising repeating units of formula (V) with X being (X-2),orreacting the compound of formula (IV) of claim 8 with a (poly)amine to obtain the polymer comprising repeating units of formula (V) with X being (X-3).

11. The method of claim 10, wherein the activated carbonic acid derivative is selected from carbonyl dichloride, carbonyl dibromide, bis(trichloromethyl) carbonate, N, N'-carbonyldiimidazole, dimethyl carbonate, diethyl carbonate, and diphenyl carbonate.

12. A polymer obtainable by reacting the compound of formula (IV) of claim 8 with a curing agent selected from an amine-based curing agent and / or a phenol-based curing agent.

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