Method for synthesis of high molecular weight polyhydroxyurethanes and polyhydroxyurethanes thereof

Abstract

Method for the synthesis of a polyhydroxyurethane (PHU) is characterized in that it comprises: a) providing cyclic carbonate monomers comprising two or more phenylene carbonate groups, b) providing amine monomers comprising two or more secondary amines moieties selected from alicyclic amines, alicyclic polyamines, or any mixture thereof; c) reacting the cyclic carbonate monomers with the amine monomers in the presence of a polar aprotic solvent under reaction conditions; and d) recovering a reaction product reaction which is a polyhydroxyurethane.

Description

[0001] METHOD FOR SYNTHESIS OF HIGH MOLECULAR WEIGHT POLYHYDROXYURETHANES AND POLYHYDROXYURETHANES THEREOF TECHNICAL FIELD

[0002] The present disclosure relates to polyhydroxyurethanes (PHUs), method for synthesis of the same, and articles made from such PHUs.

[0003] TECHNICAL BACKGROUND

[0004] Polyhydroxyurethanes (PHUs) are increasingly viewed as promising alternatives to conventional polyurethanes due to their non-toxic and environmentally friendly characteristics. PHUs are typically synthesized through the reaction of cyclic carbonates and amines, a process that avoids the use of toxic isocyanates. Despite the advantages, one of the key challenges in the development and commercialization of PHUs lies in the difficulty of producing high molecular weight polymers, which are crucial for achieving the desired mechanical and physical properties required in industrial applications like coatings, elastomers, and foams.

[0005] High molecular weight polymers are essential because they provide enhanced mechanical strength, elasticity, and durability, which are necessary for many applications where polyurethanes are traditionally used. However, several technical barriers make it difficult to synthesize PHUs with the required high molecular weight.

[0006] A primary challenge arises from the inherent chemical nature of the cyclic carbonate-amine reaction. Unlike isocyanate-based polyurethane systems, which proceed with high reactivity and lead to a controlled polymerization process, the cyclic carbonate-amine reaction tends to have slower reaction kinetics. This slower polymerization process limits the molecular weight that can be achieved in a reasonable time frame.

[0007] Achieving a high degree of polymerization is often hindered by side reactions and incomplete conversions, which can cap the molecular weight of the resulting polymer at lower levels than desired.

[0008] Another limitation is the relatively low reactivity of cyclic carbonates compared to isocyanates. Cyclic carbonates typically require higher temperatures and longer reaction times to achieve significant polymer chain growth. These conditions can lead to undesirable side reactions, including ring-opening reactions that result in cross-linked or branched structures, which in turn limit the achievable molecular weight.

[0009] Furthermore, the presence of hydroxyl groups in PHUs, which are a result of the cyclic carbonate-amine reaction, can also pose challenges. While hydroxyl groups impart beneficial properties like hydrogen bonding and increased material flexibility, they can also lead to unwanted side reactions that terminate the polymer chains prematurely. This makes it more difficult to achieve a highdegree of polymerization without introducing chain extenders or additional reactive groups, which complicates the synthesis process.

[0010] An example of PHUs synthesis is given in US2021 053953 A1 describing a compound represented by general formula (lb),

[0011]

[0012] wherein ring A is a carbocyclic or heterocyclic ring, a reaction product of the reaction between one or more said compounds and one or more amine-containing compounds, and the method to produce it.

[0013] Another example is provided by US 2023 0212355 A1 describing the method to produce the compound:

[0014]

[0015] wherein, R, R' and R" are the same or different and substitutable hydrocarbon groups, and represent an alkyl group having 1 to 12 carbon atoms, an aryl group or a heteroaryl group having 3 to 10 ring atoms, wherein the alkyl group, the aryl group, and the heteroaryl group may be substituted with substituents selected from hydroxy, amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino, or heteroaryl group, and n, m, and p are the same or different, and are integers of 1 to 10. In the disclosed method, the step of preparing the polyhydroxyurethane by reacting diamine with a dimer acid dicyclic carbonate is performed at 60 to 100° C for 2 to 24 hours.

[0016] Both methods are interesting but have low kinetics and require high temperatures.

[0017] US10,442,872 discloses a biosourced polymer obtained by dual chemical functionalization of chitosan, usable for catalytic carbonation of cyclic ethers by means of carbon dioxide, and a binder composition for creating layers and / or coatings for road construction and / or civil engineering, marking materials, or sealing or insulation materials. Said composition contains a polyhydroxyurethane polymer binder resulting from the reaction of at least one polyamine with atleast one polycyclocarbonate. Said polycyclocarbonate was obtained by carbonating a (cyclic) poly(ether) with carbon dioxide catalyzed by said biosourced polymer.

[0018] The present invention aims to provide a solution to one or more of the aforementioned needs. The invention provides high molecular weight PHUs (HMWPHUs) and a method for the synthesis thereof.

[0019] SUMMARY

[0020] Surprisingly, it has been found that the combination of cyclic carbonate monomers comprising two or more phenylene carbonate groups and amine monomers comprising two or more secondary amine moieties results in fast reaction kinetics. It has also been found that using amine monomers comprising two or more secondary amine moieties further increases the reaction rate, allowing obtaining PHUs of a higher molecular weight, either by increasing the degree of polymerization or the conversion, resulting in a more rigid polymer structure.

[0021] According to a first aspect, the invention provides a method for the synthesis of a polyhydroxyurethane (PHU) comprising:

[0022] a) providing cyclic carbonate monomers comprising two or more phenylene carbonate groups;

[0023] b) providing amine monomers comprising two or more secondary amine moieties selected from alicyclic amines, alicyclic polyamines, or any mixture thereof; c) reacting the cyclic carbonate monomers with the amine monomers in the presence of a polar aprotic solvent under reaction conditions; and

[0024] d) recovering a reaction product which is a polyhydroxyurethane.

[0025] As it can be understood from the definition given the invention is about a process to produce PHUs using specifically designed monomers that allow for producing thermoplastic HMW PHUs with a high degree of polymerization (DP) of at least 45 when monomers have a number average molecular weight (Mn) of at most 1,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC), or thermoset PHUs with a high conversion of cyclic carbonate moiety of at least 85 %.

[0026] In a first embodiment, the polyhydroxyurethane is linear, and the amine monomers comprise two secondary amine moieties and are selected from a cyclic diamine, a dicyclic diamine, and any mixture thereof.

[0027] With preference, the cyclic carbonate monomers and the amine monomers both have a number average molecular weight (Mn) of at most 1,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC); and the polyhydroxyurethane recovered in step d) has a degree of polymerization (DP) of at least 45 as determined accordingto the method of the description; more preferably a degree of polymerization ranging from 45 to 300, even more preferably a degree of polymerization ranging from 45 to 150.

[0028] Alternatively, at least one of the cyclic carbonate monomers or the amine monomers has a number average molecular weight (Mn) of more than 1,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC); and the polyhydroxyurethane recovered in step d) has a degree of polymerization (DP) of at least 10 as determined according to the method of the description; more preferably a degree of polymerization ranging from 10 to 50. For example, the degree of polymerization ranges from 10 to 40.

[0029] Preferably, the linear polyhydroxyurethane recovered in step d) has a number average molecular weight (Mn) of at least 25,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC).

[0030] In a second embodiment, the polyhydroxyurethane is cross-linked and the amine monomers comprise at least one cyclic triamine or dicyclic triamine.

[0031] With preference, the cyclic carbonate monomers in the product obtained in step d) has a conversion of at least 85 % as determined by NIR and form, at 20°C to 50°C, a gel or microgel particles.

[0032] Whatever the embodiment, one or more of the following can be used to further define the carbonate monomers.

[0033] Preferably, the carbonate monomers comprising two or more phenylene carbonate groups are selected from bis (phenylene carbonate), phenylene dicarbonates, and phenylene triscarbonate. More preferably, the carbonate monomers comprise one or more bis (phenylene carbonate) with two o-phenylene carbonate groups that are compounds of formula (2); wherein a compound of formula (2) is:

[0034]

[0035] wherein one or more aromatic rings of the o-phenylene carbonate groups are optionally functionalized with one or more selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more cycloaliphatic groups, one or more aromatic groups, one or more heterocyclo groups of 3 to 6 carbon atoms with one or more heteroatoms, one or more ortho-substituted phenyl groups, one or more meta-substitued phenyl groups, one or more parasubstituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups with one or more heteroatoms, one or more keto heteroaromatic hydrocarbon groups with one or more heteroatoms;.wherein L’ is a linker between the aromatic rings of two o-phenylene carbonate groups sharing independently one or two carbon atoms with each aromatic ring of two o-phenylene carbonate groups and that is selected from a direct bond or a structure that is or comprises one or more selected from:

[0036] one or more heteroatoms;

[0037] one or more linear or branched aliphatic chains, optionally being or comprising at least one cycloaliphatic group having from 4 to 12 carbon atoms;

[0038] one or more linear or branched alkene or polyalkene chains, optionally being or comprising at least one cycloalkene group having from 4 to 12 carbon atoms;

[0039] one or more linear or branched heteroaliphatic chains comprising one or more heteroatoms, optionally being or comprising at least one heterocyclo group of 3 to 6 carbon atoms;

[0040] one or more linear or branched heteroalkene or heteropolyalkene chains comprising one or more heteroatoms, optionally being or further comprising at least one heterocycloalkene group of 3 to 6 carbon atoms;

[0041] one or more linear or branched arylene or polyarylene chains, optionally being or comprising at least one aromatic ring;

[0042] one or more linear or branched heteroaromatic or polyheteroaromatic chains comprising one or more heteroatoms, optionally being or further comprising at least one heteroaromatic ring;

[0043] wherein the one or more heteroatoms are selected from N, S, O, and any combination thereof; wherein, when the linker comprises one or more chains, one or more carbons of the chains are optionally substituted with one or more selected from a fluorene group, one or more alkyl groups having 1 to 12 carbon atoms, one or more alkene or polyalkene groups having 1 to 12 carbon atoms, one or more hydroxy or polyhydroxy groups having 1 to 12 carbon atoms, one or more carboxylic acid groups having 1 to 12 carbon atoms; one or more ketone group, one or more cycloaliphatic groups having from 4 to 12 carbon atoms, one or more aryl groups having from 4 to 6 carbon atoms, one or more halogens groups, and any combination thereof; wherein the halogen groups are F, Cl, Br, I and any combination thereof;

[0044] wherein, when the linker comprises one or more aromatic rings or heteroaromatic rings , one or more aromatic rings or heteroaromatic rings are optionally functionalized with one or more selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more cycloaliphatic groups, one or more aromatic groups, one or more heterocyclo groups of 3 to 6 carbon atoms with one or more heteroatoms, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups with one ormore heteroatoms, one or more keto heteroaromatic hydrocarbon groups with one or more heteroatoms.

[0045] In one or more embodiments, the linker L’ is selected such that the carbonate monomers have a number average molecular weight (Mn) of at most 1,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC).

[0046] For example, the linker L’ is selected such that the carbonate monomers have a number average molecular weight (Mn) of at most 1,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC) and the carbonate monomers comprise at least one cycloaliphatic group having from 4 to 12 carbon atoms; with preference, the carbonate monomers are or comprise at least one selected from:

[0047]

[0048] o or tu

[0049] Alternatively, the linker L’ is selected such that the carbonate monomers have a number average molecular weight (Mn) ranging from more than 1000 g / mol to at most 10,000 g / mol as determined by Size exclusion chromatography (SEC) / gel permeation chromatography (GPC).

[0050] For example, the linker L’ is selected such that the carbonate monomers have a number average molecular weight (Mn) ranging from more than 1000 g / mol to at most 10,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC), and the polymeric linker L’ is a polymeric chain selected from a linear or a branched chain selected from an aliphatic chain, a polyether chain, a polyester chain, a polycarbonate chain, a diene rubber chain, and an epoxy-based linear polymer chain.

[0051] Whatever the embodiment, one or more of the following can be used to further define the amine monomers:

[0052] In one or more embodiments, the amine monomers comprise alicyclic polyamines being one or more alicyclic diamines selected from piperazine, homopiperazine, diazepane, diazinane, diazacyclooctane, diazacyclononane, diazacycloundecane, diazabicycloheptane, diazaspirooctane, diazaspirononane, diazaspirodecane, diazaspiroundecane, oxadiazaspiroundecane; and any mixture thereof; with preference, one or more cyclic diamines are selected from piperazine, homopiperazine, and any mixture thereof.In one or more embodiments, the amine monomers comprise alicyclic polyamines being one or more alicyclic diamines selected from dicyclic compounds of the formula (3), (4), and any mixture thereof,

[0053] wherein a compound of formula (3) is:

[0054] AB (3)

[0055] with A and B being each independently a nitrogen-containing cyclic structure selected from the group consisting of aziridine, aztidine, pyrrolidine, piperidine, azepane, azocane, and with A and B sharing 1 or 2 carbon atoms;

[0056] wherein a compound of formula (4) is:

[0057] A-L-B (4)

[0058] with A and B being each independently a nitrogen-containing cyclic structure selected from the group consisting of aziridine, aztidine, pyrrolidine, piperidine, azepane, azocane;

[0059] with L being a linker between A and B, selected from a direct bond or a structure that is or comprises one or more selected from:

[0060] one or more heteroatoms;

[0061] one or more linear or branched aliphatic chains, optionally being or comprising at least one cycloaliphatic group having from 4 to 12 carbon atoms;

[0062] one or more linear or branched alkene or polyalkene chains, optionally being or comprising at least one cycloalkene group having from 4 to 12 carbon atoms; one or more linear or branched heteroaliphatic chains comprising one or more heteroatoms, optionally being or comprising at least one heterocyclo group of 3 to 6 carbon atoms;

[0063] one or more linear or branched heteroalkene or heteropolyalkene chains comprising one or more heteroatoms, optionally being or further comprising at least one heterocycloalkene group of 3 to 6 carbon atoms;

[0064] one or more linear or branched arylene or polyarylene chains, optionally being or comprising at least one aromatic ring;

[0065] one or more linear or branched heteroaromatic or polyheteroaromatic chains comprising one or more heteroatoms, optionally being or further comprising at least one heteroaromatic ring;

[0066] wherein the one or more heteroatoms selected from N, S, O and any combination thereof; wherein, when the linker comprises one or more chains, one or more carbons of the chains are optionally substituted with one or more selected from a fluorene group, one or more alkyl groups having 1 to 12 carbon atoms, one or more alkene or polyalkene groups having 1 to 12 carbonatoms, one or more hydroxy or polyhydroxy groups having 1 to 12 carbon atoms, one or more carboxylic acid groups having 1 to 12 carbon atoms; one or more ketone group, one or more cycloaliphatic groups having from 4 to 12 carbon atoms, one or more aryl groups having from 4 to 6 carbon atoms, one or more halogens groups, and any combination thereof; wherein the halogen groups are F, Cl, Br, I and any combination thereof;

[0067] wherein, when the linker comprises one or more aromatic rings or heteroaromatic rings, one or more aromatic rings or heteroaromatic rings are optionally functionalized with one or more selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more cycloaliphatic groups, one or more aromatic groups, one or more heterocyclo groups of 3 to 6 carbon atoms with one or more heteroatoms, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups with one or more heteroatoms, one or more keto heteroaromatic hydrocarbon groups with one or more heteroatoms.

[0068] For example, one or more alicyclic diamines are selected from octahydro-1 H-pyrrolo[3, 4-b]pyridine; 1,3-di(piperidin-4-yl)propane, 3,3’-bipiperidine, 2,2’-bipiperidine, 4,4’-bipiperidine , and any mixture thereof.

[0069] In one or more embodiments, the linker L is selected such that the amine monomers have a number average molecular weight (Mn) of at most 1,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC).

[0070] With preference, the amine monomers comprise or are selected from piperazine, homopiperazine octahydro-1 H-pyrrolo[3,4-b]pyridine; 1,3-di(piperidin-4-yl)propane, 3,3’-bipiperidine, 2,2’-bipiperidine, 4,4’-bipiperidine , and any mixture thereof.

[0071] Alternatively, the linker L is selected such that the amine monomers have a number average molecular weight (Mn) ranging from more than 1000 g / mol to at most 10,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC); with preference, the linker L is a polymeric chain selected from a linear or a branched chain selected from an aliphatic chain, a polyether chain, a polyester chain, a polycarbonate chain, a diene rubber chain, and an epoxy-based linear polymer chain.

[0072] Whatever the embodiment, one or more of the following can be used to further define the reaction and reaction conditions

[0073] In one or more embodiments, the reaction is performed in the presence of a polar aprotic solvent wherein the carbonate monomers are provided at a concentration of at least 0.50 mol / L.

[0074] Preferably, the polar aprotic solvent selected from dimethyl sulfoxide, N-Methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, sulfolane, tetrahydrofuran, dichloromethane, chloroform,1,2,3-trichloroethane, hexamethylphosphoramide, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, 1 ,4-dioxane, acetone, methylethylketone cyclohexanone and any mixture thereof.

[0075] In a preferred embodiment, the reaction is performed at a reaction temperature ranging from 20 to 100°C.

[0076] In a preferred embodiment, the reaction is performed for a reaction time of 20 min to 12 hours. According to a second aspect, the invention provides a polyhydroxyurethane represented by one of the formulas (6) to (8)

[0077]

[0078] wherein:

[0079] - p is an integer from 10 to 300

[0080] - A and B are each independently a nitrogen-containing cyclic structure selected from the group consisting of aziridine, aztidine, pyrrolidine, piperidine, azepane, azocane; - F is a cyclic structure comprising two tertiary amines and carbon atoms,

[0081] L and L’ are linkers being the same or different and each being selected from a direct bond or a structure that is or comprises one or more selected from:

[0082] one or more heteroatoms;

[0083] one or more linear or branched aliphatic chains;

[0084] one or more linear or branched alkene or polyalkene chains;

[0085] one or more linear or branched heteroaliphatic chains comprising one or more heteroatoms;one or more linear or branched heteroalkene or heteropolyalkene chains comprising one or more heteroatoms;

[0086] one or more linear or branched arylene or polyarylene chains;

[0087] one or more linear or branched heteroaromatic or polyheteroaromatic chains comprising one or more heteroatoms;

[0088] wherein the one or more heteroatoms selected from N, S, O and any combination thereof; further wherein in formula (7) A and B share 1 or 2 carbon atoms;

[0089] with preference, the polyhydroxyurethane is synthetized by the method according to any one of the claims 1 to 16.

[0090] Preferably, the polyhydroxyurethane is represented by one of the below formulas (9) to (13)

[0091]

[0092]

[0093] wherein n is an integer from 45 to 300.

[0094] BRIEF DESCRIPTION OF THE DRAWINGS

[0095] Figure 1 shows the1H NMR spectrum of Mi in DMSO-de.

[0096] Figure 2 shows the1H NMR spectrum of M2 in DMSO-de.

[0097] Figure 3 shows the1H NMR spectrum of PHU1 in DMSO-de.

[0098] Figure 4 shows the13C NMR spectrum of PHU1 in DMSO-de.

[0099] Figure 5 shows the1H NMR spectrum of PHUe in DMSO-de.

[0100] Figure 6 shows the13C NMR spectrum of PHUe in DMSO-de.

[0101] DETAILED DESCRIPTION

[0102] When describing the invention, the terms used are to be construed in accordance with the following definitions, unless a context dictates otherwise.

[0103] As used herein, the singular forms "a", "an", and "the" include both singular and plural referents unless the context clearly dictates otherwise.

[0104] The terms "comprising", "comprises" and "comprised of" as used herein are synonymous with "including", "includes" or "containing", "contains", and are inclusive or open-ended and do not exclude additional, non-recited members, elements, or method steps. It will be appreciated that the terms "comprising", "comprises" and "comprised of" as used herein comprise the terms "consisting of", "consists" and "consists of".

[0105] The recitation of numerical ranges by endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g. 1 to 5 can include 1, 2, 3, 4, 5 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when referring to, for example, measurements). The recitation of end points also includes the endpoint values themselves (e.g. from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein.

[0106] All references cited in the present specification are hereby incorporated by reference in their entirety. In particular, the teachings of all references herein specifically referred to are incorporated by reference.Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art from this invention, in one or more embodiments. Furthermore, while some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments, as would be understood by those in the art.

[0107] In an aspect, the invention relates to a method for the synthesis of a polyhydroxyurethane (PHU) comprising:

[0108] a) providing cyclic carbonate monomers comprising two or more phenylene carbonate groups:

[0109] b) providing amine monomers comprising two or more secondary amines moieties selected from alicyclic amines, alicyclic polyamines, or any mixture thereof;

[0110] c) reacting the cyclic carbonate monomers with the amine monomers in the presence of a polar protic solvent under reaction conditions; and

[0111] d) recovering a reaction product which is a polyhydroxyurethane.

[0112] As it can be seen from the examples, the method of the invention allows for the production of polyhydroxyurethane with a high degree of polymerization (DP) or thermoset PH Us with a high conversion of cyclic carbonate monomers.

[0113] As it will be seen, the method of the invention is suitable for the production of linear polyhydroxyurethanes and for the production of crosslinked polyhydroxyurethanes.

[0114] In a first embodiment, the polyhydroxyurethane recovered in step d) is linear, and the amine monomers comprise two secondary amine moieties and are selected from a cyclic diamine, a dicyclic diamine, and any mixture thereof.

[0115] With preference, the linear polyhydroxyurethane recovered in step d) has a number average molecular weight (Mn) of at least 25,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC); preferably of at least 26,000 g / mol, more preferably, of at least 27,000 g / mol; and even more preferably of at least 28,000 g / mol. For example, the linear polyhydroxyurethane recovered in step d) has a number average molecular weight (Mn) of at most 150,000 g / mol, preferably at most 130,000 g / molAs it will be seen in detail this can be achieved with a high degree of polymerization (DP) of at least 45 when both monomers have a number average molecular weight (Mn) of at most 1 ,000 g / mol or with a degree of polymerization (DP) of at least 10 when heavy monomers are used, such as polymeric monomers.

[0116] Thus, in a preferred embodiment, the cyclic carbonate monomers and the amine monomers both have a number average molecular weight (Mn) of at most 1,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC) and the polyhydroxyurethane recovered in step d) has a degree of polymerization (DP) of at least 45 as determined according to the method of the description; preferably a degree of polymerization ranging from 45 to 300; more preferably from 46 to 250; even more preferably from 48 to 200; and most preferably from 50 to 150.

[0117] For example, the cyclic carbonate monomers and the amine monomers both have a number average molecular weight (Mn) of at most 950 g / mol, preferably at most 900 g / mol; more preferably at most 800 g / mol.

[0118] Alternatively, at least one of the cyclic carbonate monomers or the amine monomers has a number average molecular weight (Mn) of more than 1,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC) and in that the polyhydroxyurethane recovered in step d) has a degree of polymerization (DP) of at least 10 as determined according to the method of the description; preferably at least 12; more preferably at least 15; even more preferably at least 18; and most preferably at least 20.

[0119] For example, a degree of polymerization ranging from 10 to 50; preferably from 10 to 45; more preferably from 15 to 42; and even most preferably, from 20 to 40.

[0120] For example, at least one of the cyclic carbonate monomers or the amine monomers has a number average molecular weight (Mn) ranging from more than 1,000 g / mol to at most 10,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC); preferably from 1,200 to 9,000 g / mol; more preferably from 1,500 to 8,000 g / mol; even more preferably from 1,700 to 7,000 g / mol; most preferably from 2,000 to 6,000 g / mol; and even most preferably from 2,500 to 5,000 g / mol.

[0121] In a second embodiment, the polyhydroxyurethane recovered in step d) is cross-linked and the amine monomers comprise at least one cyclic triamine or dicyclic triamine.

[0122] In such a case, the cyclic carbonate monomers in the product obtained in step d) has a conversion of at least 85 % as determined by NIR and form, at 20°C to 50°C, a gel or microgel particles; preferably a conversion of at least 88 %, and even more preferably a conversion of at least 90 %.

[0123] As regards the cyclic carbonate monomers and the step a) of providing cyclic carbonate monomersPreferably, the cyclic carbonate monomers comprises two or more phenylene carbonate groups which are selected from bis(phenylene carbonate), phenylene dicarbonates, and phenylene triscarbonate.

[0124] The bis(phenylene carbonate) monomers are structures comprising two o-phenylene carbonate groups

[0125] For example, the carbonate monomers used in the method comprise one or more bis(phenylene carbonate) with two o-phenylene carbonate groups.

[0126] The o-phenylene carbonate group has the structure (1)

[0127]

[0128] Suitable bis(phenylene carbonate) with two o-phenylene carbonate groups may be of formula (2), wherein a compound of formula (2) is:

[0129]

[0130] wherein one or more aromatic rings of the o-phenylene carbonate groups are optionally functionalized with one or more selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more cycloaliphatic groups, one or more aromatic groups, one or more heterocyclo groups of 3 to 6 carbon atoms with one or more heteroatoms, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more parasubstituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups with one or more heteroatoms, one or more keto heteroaromatic hydrocarbon groups with one or more heteroatoms;

[0131] wherein L’ is a linker between the aromatic rings of two o-phenylene carbonate groups sharing independently one or two carbon atoms with each aromatic ring of two o-phenylene carbonate groups and that is selected from a direct bond or a structure that is or comprises one or more selected from:

[0132] one or more heteroatoms;

[0133] one or more linear or branched aliphatic chains, optionally being or comprising at least one cycloaliphatic group having from 4 to 12 carbon atoms;

[0134] one or more linear or branched alkene or polyalkene chains, optionally being or comprising at least one cycloalkene group having from 4 to 12 carbon atoms;one or more linear or branched heteroaliphatic chains comprising one or more heteroatoms, optionally being or comprising at least one heterocyclo group of 3 to 6 carbon atoms;

[0135] one or more linear or branched heteroalkene or heteropolyalkene chains comprising one or more heteroatoms, optionally being or further comprising at least one heterocycloalkene group of 3 to 6 carbon atoms;

[0136] one or more linear or branched arylene or polyarylene chains, optionally being or comprising at least one aromatic ring;

[0137] one or more linear or branched heteroaromatic or polyheteroaromatic chains comprising one or more heteroatoms, optionally being or further comprising at least one heteroaromatic ring;

[0138] wherein the one or more heteroatoms are selected from N, S, O and any combination thereof; wherein, when the linker comprises one or more chains, one or more carbons of the chains are optionally substituted with one or more selected from a fluorene group, one or more alkyl groups having 1 to 12 carbon atoms, one or more alkene or polyalkene groups having 1 to 12 carbon atoms, one or more hydroxy or polyhydroxy groups having 1 to 12 carbon atoms, one or more carboxylic acid groups having 1 to 12 carbon atoms; one or more ketone group, one or more cycloaliphatic groups having from 4 to 12 carbon atoms, one or more aryl groups having from 4 to 6 carbon atoms, one or more halogens groups, and any combination thereof; wherein the halogen groups are F, Cl, Br, I and any combination thereof;

[0139] wherein, when the linker comprises one or more aromatic rings or heteroaromatic rings, one or more aromatic rings or heteroaromatic rings are optionally functionalized with one or more selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more cycloaliphatic groups, one or more aromatic groups, one or more heterocyclo groups of 3 to 6 carbon atoms with one or more heteroatoms, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups with one or more heteroatoms, one or more keto heteroaromatic hydrocarbon groups with one or more heteroatoms.

[0140] In a preferred embodiment, the linker L’ is selected such that the carbonate monomers have a number average molecular weight (Mn) of at most 1,000 g / mol as determined by Size exclusion chromatography (SEC) / gel permeation chromatography (GPC).

[0141] For example, the carbonate monomers comprise at least one cycloaliphatic group having from 4 to 12 carbon atoms; with preference, the carbonate monomers are or comprise at least one selected from:

[0142]

[0143] In an alternative embodiment, the linker L’ is selected such that the carbonate monomers have a number average molecular weight (Mn) ranging from more than 1000 g / mol to at most 10,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC); with preference, the linker L’ is a polymeric chain selected from a linear or a branched chain selected from an aliphatic chain, a polyether chain, a polyester chain, a polycarbonate chain, a diene rubber chain, and an epoxy-based linear polymer chain.

[0144] For example, the diene rubber chain is selected from a polybutadiene chain, a styrene-butadiene rubber chain, a polyisoprene chain, a nitrile butadiene rubber chain, a chloroprene rubber chain an ethylene propylene diene monomer chain and their hydrogenated derivatives.

[0145] Examples of suitable compounds of formula (2) are provided below

[0146] <

[0147] <

[0148] >

[0149] <

[0150] >

[0151]

[0152] <>

[0153]

[0154] >

[0155] >

[0156]

[0157]

[0158] As it is understood by the person skilled in the art:

[0159] - In (2-1), the linker L’ is a direct bound);

[0160] - In (2-2), the linker L’ is a linear aliphatic chain of 4 carbon atoms;

[0161] - In (2-3), the linker L’ is a linear aliphatic chain of 1 carbon atom substituted with a fluorene group;

[0162] - In (2-4), the linker L’ is oxygen (i.e. a heteroatom)

[0163] - In (2-5), the linker L’ is an aliphatic chain of 1 carbon atom substituted with a ketone group (i.e. the linker L’ is a ketone group)

[0164] - In (2-6), the linker L’ is an aliphatic chain of 2 carbon atoms substituted with two ketone groups (i.e. the linker L’ is a diketone structure)

[0165] - In (2-7), the linker L’ is a structure comprising a heterodialkene chain with O as heteroatom, the chain is substituted with two ketone groups and two carboxylic acid groups

[0166] - In (2-8), the linker L’ is a structure comprising an aryl ether group (i.e. 2 heteroatom and an aromatic ring)

[0167] - In (2-9) and (2-10) the linker L’ is a heterodialkene chain, with O as the heteroatom, substituted with two ketone groups comprising a heteroaromatic group with N as heteroatom

[0168] - In (2-11) and (2-12) the linker L’ is an aliphatic chain of 2 C substituted with halogen groups being Cl

[0169] - In (2-13) the linker L’ is an aliphatic chain of one C substituted with an alkene group substituted with Cl

[0170] - In (2-14) the linker L’ is a structure comprising a branched heterodialkene chain with O as heteroatom, the chain is substituted with four ketone groups and comprises a cycloaliphatic group and a heterocyclo group

[0171] In (2-15), the linker L’ is a structure comprising two cycloaliphatic groups each sharing two carbon atoms with an aromatic ring, the two cycloaliphatic groups sharing one carbon atom, each of the cycloaliphatic group having a carbon atom that is substituted with two methyl groups.

[0172] In (2-16), the linker L’ is a structure comprising an aromatic ring sharing two carbon atoms with an aromatic ring of one of the two o-phenylene carbonate groups and that is linkedby a double bond to the aromatic rings of the other o-phenylene carbonate group, and wherein the aromatic ring is substituted on two carbon atoms with a heterocyclic group of 4 carbon atoms with O as heteroatom, the heterocyclic group being substituted with a ketone.

[0173] In (2-17), the linker L’ is a structure comprising a branched aliphatic chain comprising a cycloaliphatic group sharing two carbon atoms with an aromatic ring of one of the two o- phenylene carbonate groups.

[0174] In (2-18) to (2-20) the linker L’ can be oligomeric or polymeric.

[0175] The phenylene dicarbonate monomers are structures comprising two carbonate groups on a single aromatic ring. An example of suitable phenylene dicarbonate monomer is benzo[1 ,2-d:3,4-d']bis[1,3]dioxole-2,4,5,7 tetrone which is a structure of the below formula:

[0176]

[0177] Another example of suitable phenylene dicarbonate monomer is tetrahydroxy- 1, 4-benzoquinone biscarbonate (also known as [1,3]Dioxolo[4,5-f][1,3]benzodioxole-2,4,6,8-tetrone) which is a structure of the below formula:

[0178]

[0179] The phenylene triscarbonate (also known as Bis[1,3]dioxolo[4,5-e:4',5'-g][1,3]benzodioxole-2, 5, 8-trione) is a structure of the formula

[0180]

[0181] In an embodiment, the step a) further comprises the synthesis of the cyclic carbonate monomers, including providing monomer precursors comprising two aromatic rings, each having two adjacent carbons being substituted with hydroxy groups and reacting them with a carbonation reagent. Suitable carbonation reagents can be selected from but are not limited to: phosgene, triphosgene,dialkyl carbonare (such as dimethyl carbonate and diethylcarbonate) diarylcarbonate (such as diphenylcarboante), carbon monoxide, carbon dioxide and any mixture thereof.

[0182] For example, the step a) further comprises the synthesis of the cyclic carbonate monomers, including providing monomer precursors comprising two aromatic rings, each having two adjacent carbons being substituted with hydroxy groups and reacting them with triphosgene in the presence of triethylamine.

[0183] Examples of monomer precursors being components containing at least two ortho benzene diol moieties that can be used for the synthesis of the cyclic carbonate monomers, are selected from:

[0184]

[0185] The reaction conditions comprise a reaction temperature ranging from 0 to 50°C, preferably 0 to 25°C.

[0186] The reaction time may be from 5 to 24 hours, preferably from 7 to 18 hours.

[0187] The reaction is performed in the presence of a solvent, such as a polar aprotic solvent. For example, the solvent is selected from tetrahydrofuran (THF), diethyl ether, 1,4-dioxane, methyl tert-butyl ether (MTBE), 1,2-dimethoxyethane (DME), acetonitrile (MeCN), methylene chloride (dichloromethane, DCM), ethyl acetate and any mixture thereof. With preference, the solvent is or comprises tetrahydrofuran.Any method known for the synthesis of suitable cyclic carbonate monomers can be used. Suitable methods are for example disclosed in Hashimoto et al. in J. Org. Chem. 2021, 86, 9811-9819, in Tabarelli et al. inGreen Chem., 2017, 19, 1519, and in inTabarelli etal. Catal. Sci. Technol., 2018, 8, 1971; all being incorporated herein by reference.

[0188] As regards the diamine monomers and step b) of providing diamine monomers

[0189] According to the invention, the diamine monomers comprising two secondary amine moities, are selected from alicyclic amines, alicyclic polyamines, or any mixture thereof.

[0190] In a preferred embodiment, alicyclic polyamines are selected from alicyclic diamines, alicyclic triamines, alicyclic tetraamine, or any mixture thereof.

[0191] For example, the alicyclic diamine is or comprises one or more selected from piperazine, homopiperazine, diazepane, diazinane, diazacyclooctane, diazacyclononane, diazacycloundecane, diazabicycloheptane, diazaspiroheptane, diazaspirooctane, diazaspirononane, diazaspirodecane, diazaspiroundecane, oxadiazaspiroundecane; and any mixture thereof; with preference, the alicyclic diamine is selected from piperazine, homopiperazine, and any mixture thereof.

[0192] For example, diazabicycloheptanes with two secondary amines are 2,5-diazabicyclo [4.1.0] heptane; 2,4-diazabicyclo [3.1.1] heptane; 2,3-diazabicyclo [3.2.0] heptane; 2,4- diazabicyclo [4.1.0] heptane; and 3,4-diazabicyclo [4.1.0] heptane.

[0193] For example, daiazabicyclooctanes with two secondary amines are 2,5-diazabicyclo [4.2.0] octane; 2,6-diazabicyclo [5.1.0] octane; 2,4-diazabicyclo [3.2.1] octane; 7,8-diazabicyclo [4.2.0] octane; (7S)-2,6-diazabicyclo [5.1.0] octane; (1R,6R)-2,5-diazabicyclo [4.2.0] octane; 2,5-diazabicyclo [5.1.0] octane; (1S,6S)-2,5-diazabicyclo [4.2.0] octane; 2,5-diazabicyclo [4.1.1] octane; 6,7-diazabicyclo [3.2.1] octane; and 2,3-diazabicyclo [4.2.0] octane.

[0194] For example, diazabicyclononanes with two secondary amines are 2,6-diazabicyclo [6.1.0] nonane; 2,5-diazabicyclo [4.2.1] nonane; 2,4-diazabicyclo [3.3.1] nonane; 2,7-diazabicyclo [6.1.0] nonane: 2,5-diazabicyclo [5.1.1] nonane; 2,5-diazabicyclo [5.2.0] nonane; 2,5-diazabicyclo [6.1.0] nonane; 2,6-diazabicyclo [5.2.0] nonane; 2,6-diazabicyclo [5.1.1] nonane; 3,5-diazabicyclo [5.2.0] nonane; and 2,4-diazabicyclo [5.2.0] nonane.

[0195] For example, diazaspiroheptanes with two secondary amines are 1,2-diazaspiro [2.4] heptane; 1,2-diazaspiro [3.3] heptane; 5,6-diazaspiro [2.4] heptane; and 4,6-diazaspiro [2.4] heptane. For example, diazaspirooctanes with two secondary amines are 1,2-diazaspiro [2.5] octane; 1,3-diazaspiro [3.4] octane; 4,6-diazaspiro [2.5] octane; 5,7-diazaspiro [2.5] octane; 5,7-diazaspiro [3.4] octane; 5,6-diazaspiro [2.5] octane; 1,2-diazaspiro [3.4] octane; and 6,7-diazaspiro [3.4] octane.For example, diazaspirononanes with two secondary amines are 5,8-Diazaspiro [2.6] nonane; 1,2-Diazaspiro [4.4] nonane; 5,8-Diazaspiro [3.5] nonane; 4,7-Diazaspiro [2.6] nonane; 6,8-Diazaspiro [3.5] nonane; 6,7-Diazaspiro [2.6] nonane; 1,3-Diazaspiro [4.4] nonane; 1,1-Diazaspiro [2.6] nonane; 1,4-Diazaspiro [4.4] nonane; and 4,8-Diazaspiro [2.6] nonane.

[0196] For example, diazaspirodecanes with two secondary amines are 1,4-diazaspiro [4.5] decane; 6,9-diazaspiro [4.5] decane; 1,2-diazaspiro [4.5] decane; 5,8-diazaspiro [3.6] decane; 6,7-diazaspiro [4.5] decane; 5,8-diazaspiro [2.7] decane; 1,3-diazaspiro [4.5] decane; 6,9-diazaspiro [3.6] decane; 4,7-diazaspiro [2.7] decane; 4,8-diazaspiro [2.7] decane; 5,9-diazaspiro [2.7] decane; 5.9-diazaspiro [3.6] decane; 4,9-diazaspiro [2.7] decane; 1,2-diazaspiro [2.7] decane; 1,2-diazaspiro [3.6] decane; 7,9-diazaspiro [4.5] decane; and 2,3-diazaspiro [4.5] decane.

[0197] For example, diazaspiroundecanes with two secondary amines are 1,4-Diazaspiro [5.5] undecane; 1,2-Diazaspiro [5.5] undecane; 6,10-Diazaspiro [4.6] undecane, 1,3-Diazaspiro [5.5] undecane; 7,10-Diazaspiro [4.6] undecane; 7,9-Diazaspiro [4.6] undecane; 6,3-Diazaspiro [4.6] undecane; 1,2-Diazaspiro [2.8] undecane; 1,2-Diazaspiro [3.7] undecane; 6,9-Diazaspiro [3.7] undecane; 5,9-Diazaspiro [3.7] undecane; 5,10-Diazaspiro [3.7] undecane; 6,10-Diazaspiro [3.7] undecane; 1,2-Diazaspiro [4.6] undecane; 5.8-Diazaspiro [3.7] undecane; 2,4-Diazaspiro [5.5] undecane; and 1,5-Diazaspiro [5.5] undecane.

[0198] For example, oxadiazaspiroundecanes with two secondary amines are 9-oxa-1,4-diazaspiro [5.5] undecane; 8-oxa-1,4-diazaspiro [5.5] undecane; 2-oxa-5,9-diazaspiro [3.7] undecane; 1-oxa- 6.10-diazaspiro [3.7] undecane; 2-oxa-6,10-diazaspiro [4.6] undecane; 2-oxa-5,8-diazaspiro [3.7] undecane; 2-oxa-6,9-diazaspiro [4.6] undecane; 2-oxa-6,10-diazaspiro [3.7] undecane; 2-oxa- 7.10-diazaspiro [3.7] undecane; 2-oxa-5,10-diazaspiro [3.7] undecane; 1-oxa-7,10-diazaspiro [4.6] undecane; 1-oxa-7,10-diazaspiro [3.7] undecane; and 2-oxa-7,10-diazaspiro [4.6] undecane.

[0199] In an embodiment, the alicyclic diamine is dicyclic and is a compound of the formula (3), (4) and any mixture thereof,

[0200] wherein a compound of formula (3) is:

[0201] AB (3)

[0202] with A and B being each independently a nitrogen-containing cyclic structure selected from the group consisting of aziridine, aztidine, pyrrolidine, piperidine, azepane, azocane, and with A and B sharing 1 or 2 carbon atoms;

[0203] wherein a compound of formula (4) is:

[0204] A-L-B (4)

[0205] with A and B are each independently a nitrogen-containing cyclic structure selected from the group consisting of aziridine, aztidine, pyrrolidine, piperidine, azepane, azocane;with L is a linker between A and B, selected from a direct bond or a structure that is or comprises one or more selected from:

[0206] one or more heteroatoms;

[0207] one or more linear or branched aliphatic chains, optionally being or comprising at least one cycloaliphatic group having from 4 to 12 carbon atoms;

[0208] one or more linear or branched alkene or polyalkene chains, optionally being or comprising at least one cycloalkene group having from 4 to 12 carbon atoms;

[0209] one or more linear or branched heteroaliphatic chains comprising one or more heteroatoms, optionally being or comprising at least one heterocyclo group of 3 to 6 carbon atoms;

[0210] one or more linear or branched heteroalkene or heteropolyalkene chains comprising one or more heteroatoms, optionally being or further comprising at least one heterocycloalkene group of 3 to 6 carbon atoms;

[0211] one or more linear or branched arylene or polyarylene chains, optionally being or comprising at least one aromatic ring;

[0212] one or more linear or branched heteroaromatic or polyheteroaromatic chains comprising one or more heteroatoms, optionally being or further comprising at least one heteroaromatic ring;

[0213] wherein the one or more heteroatoms selected from N, S, O and any combination thereof; wherein, when the linker comprises one or more chains, one or more carbons of the chains are optionally substituted with one or more selected from a fluorene group, one or more alkyl groups having 1 to 12 carbon atoms, one or more alkene or polyalkene groups having 1 to 12 carbon atoms, one or more hydroxy or polyhydroxy groups having 1 to 12 carbon atoms, one or more carboxylic acid groups having 1 to 12 carbon atoms; one or more ketone group, one or more cycloaliphatic groups having from 4 to 12 carbon atoms, one or more aryl groups having from 4 to 6 carbon atoms, one or more halogens groups, and any combination thereof; wherein the halogen groups are F, Cl, Br, I and any combination thereof;

[0214] wherein, when the linker comprises one or more aromatic rings or heteroaromatic rings, one or more aromatic rings or heteroaromatic rings are optionally functionalized with one or more selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more cycloaliphatic groups, one or more aromatic groups, one or more heterocyclo groups of 3 to 6 carbon atoms with one or more heteroatoms, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups with one or more heteroatoms, one or more keto heteroaromatic hydrocarbon groups with one or more heteroatoms.In a preferred embodiment, the linker L is selected such that the amine monomers have a number average molecular weight (Mn) of at most 1,000 g / mol as determined by Size exclusion chromatography (SEC) / gel permeation chromatography (GPC).

[0215] Alternatively, the linker L is selected such that the amine monomers have a number average molecular weight (Mn) ranging from more than 1000 g / mol to at most 10,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC); with preference, the linker L is a polymeric chain selected from a linear or a branched chain selected from an aliphatic chain, a polyether chain, a polyester chain, a polycarbonate chain, a diene rubber chain, and an epoxy-based linear polymer chain.

[0216] A polyether chain is herein defined as a chain having repeating units being ether groups (-O-) connecting two carbon atoms. The general structure of the repeating unit is -R-O-R-, where R is an alkyl group or an aryl group.

[0217] A polyester chain is herein defined as a chain having repeating units being ester linkages (-COO-) between two carbon atoms. The general structure of the repeating unit is:

[0218]

[0219] being an alkyl or aryl group.

[0220] An example of an alicyclic diamine being bicyclic and with a polyester chain is provided below:

[0221]

[0222] A polycarbonate chain is herein defined as a chain having repeating units being carbonate groups (-O-C(=O)-O-) linking two carbon atoms. The general structure of the repeating unit is O-C(=O)-O-R-, where R can be an alkyl or aromatic group.

[0223] A diene rubber is a polymer or copolymer derived from one or more conjugated diene monomers, the general structure of the repeating unit is [-CR=CH-CR=CH-]n where R can independently be hydrogen, alkyl, aryl, or substituted alkyl / aryl groups.

[0224] A diene rubber can include homopolymers of diene monomers or copolymers with other monomers such as vinyl aromatic compounds, acrylonitrile, or other ethylenically unsaturated monomers. A diene rubber may include cis-1,4, trans-1,4, or 1 ,2-vinyl configurations. A dienerubber may include random, block, or graft copolymer architectures if additional monomers are present.

[0225] For example, a butadiene-nitrile rubber chain is herein defined as a chain consisting of alternating butadiene (a diene) and acrylonitrile (a nitrile) groups. The general structure of the repeating unit

[0226]

[0227] A epoxy-based linear polymer chain is herein defined as a chain consisting repeating units with an epoxy group in the backbone wherein the epoxy group is an oxygen atom bonded to two adjacent carbon atoms, forming a three-membered ring structure.

[0228] An example of suitable compound of formula (3) is octahydro-1 H-pyrrolo[3,4-b]pyridine of formula (5):

[0229]

[0230] (4-1)

[0231] and 3,3’-bipiperidine, 2,2’-bipiperidine and 4,4’-bipiperidine of formula (4-2)

[0232]

[0233] (4-2)

[0234] With preference the dicyclic diamine is selected from octahydro-1 H-pyrrolo[3,4-b]pyridine; 1,3-di(piperidin-4-yl)propane, 3,3’-bipiperidine, 2,2’-bipiperidine, 4,4’-bipiperidine , and any mixture thereof.

[0235] In an embodiment the diamine monomers are selected from piperazine, homopiperazine octahydro-1 H-pyrrolo[3,4-b]pyridine; 1,3-di(piperidin-4-yl)propane, 3,3’-bipiperidine, 2,2’-bipiperidine, 4,4’-bipiperidine , and any mixture thereof.

[0236] As regards the step c) of reacting the cyclic carbonate monomers with the diamine monomers1

[0237] The step c) of reacting the cyclic carbonate monomers with the diamine monomers, is performed in the presence of a solvent under reaction conditions. With preference, the reaction is performed in the presence of a solvent being a polar aprotic solvent.

[0238] For example, the polar aprotic solvent is selected from dimethyl sulfoxide (DMSO), N-Methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), sulfolane, tetrahydrofuran (THF), dichloromethane, chloroform, 1,2,3-trichloroethane, Hexamethylphosphoramide (HMPA), 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, 1,4-dioxane, acetone, methylethyl ketone cyclohexanone, and any mixture thereof.

[0239] For example, the cyclic carbonate monomers are provided at a concentration of at least 0.50 mol / L; preferably at least 0.60 mol / L; more preferably at least 0.70 mol / L.

[0240] The reaction conditions preferably include a reaction temperature ranging from 20 to 100°C: preferably ranging from 20 to 80°C: more preferably, from 30 to 70°C, and even more preferably from 40 to 60°C.

[0241] The reaction conditions preferably include a reaction time of 20 to 12 hours. For example, the reaction time is at most 360 minutes; preferably at most 250 minutes; more preferably at most 200 minutes; even more preferably at most 180 minutes; most preferably at most 160 minutes; and even most preferably at most 140 minutes.

[0242] Increasing temperature and / or time may allow for an increase in the degree of polymerization or the conversion.

[0243] As regards the polyhydroxyurethane obtained

[0244] The invention also provides for a polyhydroxyurethane prepared by the disclosed method.

[0245] In an aspect, the invention provides a polyhydroxyurethane (such as prepared by the disclosed method) that is represented by one of the below formulas (6) to (8)

[0246]

[0247]

[0248] wherein

[0249] p is an integer from 10 to 300; preferably from 10 to 50 or from 45 to 300.

[0250] A and B are each independently a nitrogen-contoaining cyclic structure selected from the group consisting of aziridine, aztidine, pyrrolidine, piperidine, azepane, azocane;

[0251] F is a cyclic structure comprising two tertiary amines and carbon atoms,

[0252] L and L’ are linkers being the same or different and each being selected from a direct bond or a structure that is or comprises one or more selected from:

[0253] one or more heteroatoms;

[0254] one or more linear or branched aliphatic chains, optionally being or comprising at least one cycloaliphatic group having from 4 to 12 carbon atoms;

[0255] one or more linear or branched alkene or polyalkene chains, optionally being or comprising at least one cycloalkene group having from 4 to 12 carbon atoms;

[0256] one or more linear or branched heteroaliphatic chains comprising one or more heteroatoms, optionally being or comprising at least one heterocyclo group of 3 to 6 carbon atoms;

[0257] one or more linear or branched heteroalkene or heteropolyalkene chains comprising one or more heteroatoms, optionally being or further comprising at least one heterocycloalkene group of 3 to 6 carbon atoms;

[0258] one or more linear or branched arylene or polyarylene chains, optionally being or comprising at least one aromatic ring;

[0259] one or more linear or branched heteroaromatic or polyheteroaromatic chains comprising one or more heteroatoms, optionally being or further comprising at least one heteroaromatic ring;

[0260] wherein the one or more heteroatoms selected from N, S, O and any combination thereof; wherein, when the linker comprises one or more chains, one or more carbons of the chains are optionally substituted with one or more selected from a fluorene group, one or more alkyl groups having 1 to 12 carbon atoms, one or more alkene or polyalkene groups having 1 to 12 carbon atoms, one or more hydroxy or polyhydroxy groups having 1 to 12 carbon atoms, one or more carboxylic acid groups having 1 to 12 carbon atoms; one or more ketone group, one or more cycloaliphatic groups having from 4 to 12 carbon atoms, one or more aryl groups having from 4to 6 carbon atoms, one or more halogens groups, and any combination thereof; wherein the halogen groups are F, Cl, Br, I and any combination thereof;

[0261] wherein when the linker comprises one or more aromatic rings or heteroaromatic rings, one or more aromatic rings or heteroaromatic rings are optionally functionalized with one or more selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more cycloaliphatic groups, one or more aromatic groups, one or more heterocyclo groups of 3 to 6 carbon atoms with one or more heteroatoms, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups with one or more heteroatoms, one or more keto heteroaromatic hydrocarbon groups with one or more heteroatoms;

[0262] optionally, wherein one or more aromatic rings functionalized with one or more selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more cycloaliphatic groups, one or more aromatic groups, one or more heterocyclo groups of 3 to 6 carbon atoms with one or more heteroatoms, one or more ortho-substituted phenyl groups, one or more metasubstituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups with one or more heteroatoms, one or more keto heteroaromatic hydrocarbon groups with one or more heteroatoms; further wherein in formula (7), A and B share 1 or 2 carbon atoms.

[0263] In an embodiment, the linker L and / or the linker L’ is a polymeric chain selected from a linear or a branched chain selected from an aliphatic chain, a polyether chain, a polyester chain, a polycarbonate chain, a diene rubber chain, and an epoxy-based linear polymer chain.

[0264] For example, the diene rubber chain is selected from a polybutadiene chain, a styrene-butadiene rubber chain, a polyisoprene chain, a nitrile butadiene rubber chain, a chloroprene rubber chain an ethylene propylene diene monomer chain.

[0265] In a preferred embodiment, the polyhydroxyurethane (such as prepared by the disclosed method) is represented by one of the below formulas (9) to (13)

[0266]

[0267]

[0268] wherein n is an integer from 45 to 300; preferably from 46 to 250; even more preferably from 48 to 200; and most preferably from 50 to 150.

[0269] The invention is remarkable in that it allows for obtaining polyhydroxyurethanes of high molecular weight.

[0270] For example, the polyhydroxyurethanes have a number average molecular weight (Mn) of at least 25,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC); preferably at least 26,000 g / mol; more preferably at least 27,000 g / mol; and even more preferably at least 28,000 g / mol. For example, the polyhydroxyurethanes of theinvention have a number average molecular weight (Mn) of at most 150,000 g / mol, preferably at most 130,000 g / mol.

[0271] For example, the polyhydroxyurethanes have a molecular weight distribution (Mw / Mn) of at least 1.9 as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC); preferably ranging from 1.9 to 3.6.

[0272] For example, the polyhydroxyurethanes have a Tg of at least 180°C as determined by TMA with a heating rate of 5°C / min; preferably at least 185°C; more preferably at least 190°C.

[0273] Examples

[0274] It is to be understood that, while the invention has been described in conjunction with the specific embodiments thereof, the foregoing description is intended to illustrate and not limit the scope of the invention. Other aspects and advantages will be apparent to those skilled in the art to which the invention pertains.

[0275] Therefore, the following examples are put forth so as to provide guidance on how to make the compounds of the invention and are not intended to limit the scope of the invention.

[0276] Materials

[0277] 5,5',6,6'-Tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane (97 %, BLD Pharmatech), 4,4'-(9H-fluorene-9,9-diyl)bis(benzene-1,2-diol) (98 %, BLD Pharmatech), triethylamine (> 99 %, Sigma-Aldrich), bis(trichloromethyl)carbonate (> 96 %, Sigma-Aldrich), phosphorous pentoxide (immobilized on silica, with indicator, Sicapent®, Sigma-Aldrich), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, 99.9 %, Solvionic), sodium hydroxide (> 98 %, Carl Roth) were used as received.

[0278] Diethylamine (> 99.5 %, Sigma-Aldrich), diisopropylamine (> 99.5 %, Sigma-Aldrich), diisobutylamine (99 %, Sigma-Aldrich), dicyclohexylamine (99 %, Sigma-Aldrich), N-methylaniline (> 98 %, TCI Europe), N-methylcyclohexylamine (> 99 %, TCI Europe), azetidine (98 %, BLD Pharmatech), pyrrolidine (> 99.5 %, Sigma-Aldrich), piperidine (> 99.5 %, Sigma-Aldrich), hexamethyleneimine (99 %, Sigma-Aldrich), 2,2,6,6-tetramethylpiperidine (98 %, BLD Pharmatech) were used for model reactions and were vacuum distilled with sodium hydroxide before using.

[0279] Piperazine (> 98 %, TCI Europe), homopiperazine (98 %, BLD Pharmatech), 1 ,3-di(piperidin-4-yl)propane (98 %, BLD Pharmatech), octahydro-1 H-pyrrolo[3,4-b]pyridine (97 %, BLD Pharmatech), N1,N3-dimethylpropane-1,3-diamine (98 %, BLD Pharmatech), N,N'-dicyclohexyl-1,2-ethanediamine (> 98 %, TCI Europe), 3,3'-bipiperidine ( > 95 %, BLD Pharmatech) were used for polymerization and were vacuum distilled with sodium hydroxide before using.Solvents: isopropanol (> 99.5 %, SLR, Extra Pure, Fisher Scientific (Acros Organics)), methanol (> 99.5 %, Fisher Scientific (Acros Organics)), tetrahydrofuran (THF, 99.6 %, Fisher Scientific (Acros Organics)), dichloromethane (> 99.5 %, Fisher Scientific (Acros Organics)), diethyl ether (99+ %, Fisher Scientific (Acros Organics)), dimethylsulfoxide (DMSO, > 99.9 %, anhydrous, Sigma-Aldrich), 1-methyl-2-pyrrolidone (NMP, 99.5 %, Extra Dry, AcroSeal, Fisher Scientific (Acros Organics)), dimethylformamide (99.7 %, HPLC grade, Fisher Scientific (Acros Organics)), dimethylformamide (99 %, extra pure, Fisher Scientific (Acros Organics)), N,N-dimethylacetamide (99.5 %, Fisher Scientific (Acros Organics)), sulfolane (99 %, Sigma-Aldrich), hexamethylphosphoramide (> 98 %, Sigma Aldrich), acetone (technical grade, Fisher Scientific (Acros Organics)), chloroform (99 %, Fisher Scientific (Acros Organics)), 1,1,2-trichloroethane (97 %, Sigma-Aldrich), acetonitrile (99.9 %, Extra Dry over Molecular Sieve, AcroSeal™, Fisher Scientific (Acros Organics)), cyclohexane, (99.5 %, Sigma-Aldrich), cyclohexanone (99.8 %, extra pure, Fisher Scientific (Acros Organics)), ethyl acetate (99.9 %, Fisher Scientific (Acros Organics)), toluene (99+ %, Fisher Scientific (Acros Organics)), dioxane (> 99.5 %, Carl Roth) were procured and used as it is. Tetrahydrofuran (THF, 99.6 %, Fisher Scientific (Acros Organics)) used to synthesize cyclic carbonates was dried through SPS (M BRAUN, SPS-800 ) system before use. Ultrapure deionized water was obtained using Sartorius Arium® Comfort smart station.

[0280] NMR solvents and standards: dimethyl sulfoxide-de (DMSO-de, 99.9 atom%D, Sigma-Aldrich) was dried over 3 molecular sieves.

[0281] Gases: argon alpha gas 2 (99.99999 %, Air Liquid).

[0282] Methods

[0283] Nuclear magnetic resonance (NMR) spectra were recorded on Avance III HD 600MHz (Bruker) spectrometer (1H NMR at 600 MHz,13C NMR at 151 MHz) at 25°C (unless stated otherwise) in the indicated deuterated solvent and are listed in ppm. The signals corresponding to the residual protons and carbons of the deuterated solvent were used as an internal standard for1H and13C NMR, respectively. Traces of common non-deuterated solvents and impurities were identified according to Fulmer et al. (Organometallics 2010, 29 (9), 2176-2179. https: / / doi.org / 10.1021 / om1001Q6e)

[0284] Size exclusion chromatography (SEC) / gel permeation chromatography (GPC) was used to determine the number-average molecular weights ( / Wn(GPC)) and MJMnratios in accordance with ASTM 5296-11 standard. The study was performed on a 1200 Infinity gel permeation chromatograph (Agilent Technologies, USA) equipped with PLgel 5pm MIXED-D column (Agilent Technologies, USA), PLgel 5pm (Agilent Technologies) pre-column and an integrated refractive index detector. The system was operated at 50°C and 1.0 mL / min flow using 0.1 M L CFsSCh^N (LiTFSI) solution in DMF as an eluent. Poly(methyl methacrylate) standards (EasiVial PM, Agilent Technologies, Mp= 550 - 1558x103) were used to perform calibration.Determination of molecular weights by sedimentation-diffusion analysis was performed using a Beckman XLI analytical ultracentrifuge (ProteomeLabTM Protein Characterization System) in a two-sector cell with an optical path length of 12 mm at a rotor speed of 40,000 rpm. To account for the concentration dependence of the sedimentation coefficient, experiments were conducted at three solution concentrations ranging from 0.38 to 0.1 g / dL. The sedimentation coefficients So at infinite dilution were calculated from the plot described by the formula:

[0285] s’1=so’1(1+sc) (1) where s - the sedimentation coefficient at a given concentration, and ks- the Gralen concentration coefficient.

[0286] Translational diffusion was studied using a Tsvetkov polarization-interferometric diffusometer at concentrations of 0.06 g / dL. Viscosimetric studies were conducted in an Ostwald capillary viscometer over a range of concentrations corresponding to relative flow times of the solution and solvent of 2-1.15. The intrinsic viscosity values were calculated from Huggins and Kraemer plots, and they matched.

[0287] Absolute molecular masses were calculated using the Svedberg equation with the obtained experimental values of So, Do M (1-upo):

[0288]

[0289] where So - the sedimentation coefficient at infinite dilution, Do - the translational diffusion coefficient, R - the gas constant, u - the partial specific volume of macromolecules, po - the solvent density, T - the absolute temperature in K, (1-upo) - is the buoyancy factor, determined densitometrically.

[0290] The errors in determining the primary experimental values are no more than 1-2%, and for the molecular mass the error is 4%.

[0291] Thermal gravimetric analysis (TGA) of polymer samples was performed in accordance with ASTM E2550-17 standard. TGA was carried out in air on a TGA2 STARe System (Mettler Toledo) applying a heating rate of 5°C / min. The onset weight loss temperature (Tonset) was determined at 0.5 wt% in accordance with the aforementioned standard, and then rounded to the nearest 5°C. The 5% of weight loss temperature (Ts%) was determined at 5 wt% in accordance with the aforementioned standard, and then rounded to the nearest 5°C.

[0292] Differential Scanning Calorimetry (DSC) was performed in accordance with ASTM D3418-21 standard. Samples were hermetically sealed in Al pans in air and the analysis was performed on a DSC 300 Caliris Select differential calorimeter (NETZSCH) in the range of -50°C to 260°C. Two heating-cooling cycles with a heating rate of 5°C / min were carried out for each sample under N2 atmosphere. Glass transition (Tg) and melting temperatures (Tm) were determined from theheating curve during the second heating cycle, while crystallization temperature (Tcr) was identified from the second cooling curve. For simplicity Tmand Tcrwere taken from the peak maximum.

[0293] Dynamic Mechanical Thermal Analysis (DMTA) was performed in accordance with the ASTM D4065-20 standard. Measurements were carried out on bars (typical length x width x thickness = 25 x 5.5 x 1.5 mm) with a DMA GABO Eplexor model (Netzsch) operating in tension mode (static strain: 2 %, dynamic strain: 0.5 %, contact force: 0.80 N). Experiments were performed at 1 Hz frequency with a heating rate of 5°C / min from -30 to 190°C in air. The setup provided the storage and loss moduli (E’ and E”). The damping parameter or loss factor (tan 5) was defined as the ratio tan 5 = E E’.

[0294] Degree of polymerization (Dpn) was calculated using the following formula:

[0295]

[0296] Where Mnis the number average molecular weight of PHU polymer determined using GPC, Mcc is the molecular weight of cyclic dicarbonate monomer and Mamine is the molecular weight of amine monomer used in the synthesis of respective PHU polymer.

[0297] The conversion of the amine during the reaction is assessed by near-infrared (NIR) following a procedure adapted from (A. Rigail-Cedeho, C.S.P. Sung, Fluorescence and IR characterization of epoxy cured with aliphatic amines, Polymer (Guildf). 46 (2005) 9378-9384. doi: 10.1016 / j.polymer.2005.04.063.).

[0298] With the following adaptation wherein the near-infrared characterization (NIR) was performed using a IN VEN IO R Fourier IR- spectrometer (Bruker, Germany) with 64 scans collected at a resolution of 8 cm-1, to produce spectra covering 7500 to 3500 cm-1(1333 nm to 2857 nm). The freshly prepared solution of monomers was poured into a mold consisting of two glass plates (microscope slides, 25x25 mm, AT-M7300-61043, Agilent Technologies, USA) separated by U- shaped 1 mm thick Teflon spacer.

[0299] The extent of reaction by NIR - QNIR is defined as follows:

[0300] aNIR=1—"T (4)

[0301] where Atis the peak area of the absorbance at -6340-6545 cm-1corresponding to secondary amine moiety at a given moment of time and Ao is the peak area of the absorbance at -6340-6545 cm-1at a t = 0 s (beginning of the reaction, measured directly after the mixing of components).

[0302] Example 1 : Synthesis and characterization of cyclic carbonates.Exemple 1.1 : 7,7,7',7'-tetramethyl-6,6',7,7'-tetrahvdro-5,5'-spirobinndenof5,6-din,31dioxole1-2,2'-dione (Mi).

[0303]

[0304] Scheme 1. Synthesis of 7,7,7',7'-tetramethyl-6,6',7,7'-tetrahydro-5,5'-spirobi[indeno[5,6-d][1,3]dioxole]-2,2'-dione (Mi).

[0305] 5,5',6,6'-Tetrahydroxy-3,3,3',3'-tetramethyl-1,T-spirobiindane (10 g, 29.4 mmol) was dissolved in 200 ml of anhydrous THF in a 2-neck round bottom flask flushed with argon. Triethylamine (18 mL, 13.08 g, 129.3 mmol) was added to the solution via syringe and the resulting mixture was cooled to 0°C using ice bath. The mixture was kept under inert atmosphere by slowly purging argon through the flask. Then bis(trichloromethyl) carbonate (6.39 g, 21.5 mmol, 1.1 equiv. per functional group) dissolved in 50 mL of anhydrous THF was added dropwise to the stirred solution. The reaction was stirred for at least 8 hours slowly allowing it to reach room temperature (ca.

[0306] 22°C). Then the yellowish precipitate of triethylammonium chloride was removed by filtration and washed with two portions of regular THF (50 mL each). The combined THF solutions were evaporated to dryness in vacuum and the crude mixture was redissolved in DCM. The final product was obtained overnight in the form of white crystalline powder by recrystallization from DCM / diethyl ether mixture in freezer (-18°C). It was isolated by filtration, washed by diethyl ether and dried in vacuum (< 0.5 mbar) at 80°C overnight. Yield: 7.8 g (67.7%). Tonset (TGA, 5°C / min, on air) = 230°C; Tonset (TGA, 5°C / min, N2) = 275°C. Melting point (DSC, 5°C / min, clamped under N2) Tm= 269.3°C. Crystallization (DSC, 5°C / min, clamped under N2) Tc= 147.3°C. Anal, calcd. for C23H2o06(392.41): C, 70.40%; H, 5.14%; O, 24.46%. Found: C, 70.36%; H, 5.19%.

[0307] 1H NMR (600 MHz, DMSO-d6) 57.46 (s, 2H), 6.79 (s, 2H), 2.38 (d, J= 13.1 Hz, 2H), 2.20 (d, J = 13.0 Hz, 2H), 1.41 (s, 6H), 1.32 (s, 6H).

[0308] 13C NMR (151 MHz, DMSO-d6) 5 151.33. 148.32, 145.51, 142.57, 142.37, 105.80, 104.59, 58.47, 57.64, 43.47, 31.34, 29.84.

[0309] Example 1.2: 5,5'-(9H-fluorene-9,9-diyl)bis(benzofdin,31dioxol-2-one) (M2).

[0310]

[0311] Scheme 2. Synthesis of 5,5'-(9H-fluorene-9,9-diyl)bis(benzo[d][1,3]dioxol-2-one) (M2).

[0312] 5,5'-(9H-fluorene-9,9-diyl)bis(benzo[d][1 ,3]dioxol-2-one) (M2) was prepared in a similar manner to Mi. The following amounts of 4,4'-(9H-fluorene-9,9-diyl)bis(benzene-1,2-diol) (10 g, 26.1 mmol), triethylamine (16 mL, 11.64 g, 115.1 mmol) and bis(trichloromethyl) carbonate (5.69 g, 1.92 mmol, 1.1 equiv. per functional group) were used. The target compound was obtained in the form of white crystals. Yield: 10.05 g (88.5%). Tonset (TGA, 5°C / min, on air) = 250°C. Melting point (DSC, 5°C / min, clamped under N2) Tm= 240°C.

[0313] 1H NMR (600 MHz, DMSO-d6) 5 7.97 (d, J = 7.6 Hz, 2H), 7.54 (d, J = 7.6 Hz, 2H), 7.45 (td, J = 7.5, 1.0 Hz, 2H), 7.36 (dd, J= 8.6, 7.2 Hz, 4H), 7.22 (d, J= 1.9 Hz, 2H), 6.96 (dd, J= 8.5, 1.9 Hz, 2H).

[0314] 13C NMR (151 MHz, DMSO-d6) 5 150.94, 150.55, 149.41, 143.12, 142.32, 142.04, 139.39, 139.35, 128.30, 128.21, 127.87, 127.74, 126.09, 125.99, 123.54, 120.88, 120.55, 110.10, 109.97, 109.94, 64.63, 64.23.

[0315] Example 2: Synthesis of PHU polymers

[0316] General method:

[0317] Polymerization was performed in a conical 3-neck flask equipped with a mechanical stirrer. Cyclic dicarbonate (3 mmol) and diamine (3 mmol) monomers were charged inside under the flow of argon followed by 2 mL of anhydrous DMSO. The mixture was heated to 50°C using oil bath and stirred at this temperature for 3 hours. Then the heating was switched off and resulting very viscous mixture was diluted with 40 mL of THF and stirred until complete dissolution of polymer. The polymer was isolated by precipitation into isopropanol. It was further collected, washed with 10-15 mL of methanol and dried in vacuum (<0.5 mbar) at 100°C overnight.

[0318] Example 2.1: Synthesis of PHU based on Mi and piperazine (PHU1).

[0319]

[0320] Scheme 3. Synthesis of PHU1 polymer.

[0321] The following amounts were used: Mi (1.175 g, 3 mmol) and piperazine (0.258 g, 3 mmol). Yield: 1.38 g (96 %). Mn(GPC) = 105400 g mol-1, Mw / Mn= 3.6, Dpn= 220. MSD (ultracentifugation) = 71200 g mol"1. Tonset (TGA, 5°C / min, on air) = 220°C; Tonset (TGA, 5°C / min, N2) = 225°C. Tg(TMA in He, 5°C / min) = 253°C.

[0322] 1H NMR (600 MHz, DMSO-d6) 5 9.44 - 9.11 (m, 2H), 6.93 - 6.61 (m, 2H), 6.42 - 6.17 (m, 2H), 3.53 (d, J= 85.5 Hz, 8H), 2.20 (d, J= 102.0 Hz, 4H), 1.43- 1.11 (m, 12H).13C NMR (151 MHz, DMSO-d6) 6 153.04, 152.92, 149.41, 149.25, 148.69, 148.56, 148.45, 147.87, 147.57, 142.22, 142.08, 140.40, 140.03, 138.61, 138.52, 118.10, 116.32, 111.11, 109.47, 59.26, 56.85, 56.47, 56.06, 43.99, 43.27, 42.89, 42.68, 42.44, 31.44, 31.32, 31.28, 30.40, 30.36, 30.15, 30.12.

[0323] Example 2.2: Synthesis of PHU based on Mi and homopiperazine (PHU2).

[0324]

[0325] Scheme 4. Synthesis of PHU2 polymer.

[0326] The following amounts were used: Mi (1.175 g, 3 mmol) and homopiperazine (0.3 g, 3 mmol). Yield: 1.29 g (87 %). Mn(GPC) = 95300 g mo1, Mw / Mn= 2.8, Dpn= 194. Tonset (TGA, 5°C / min, on air) = 200°C; Tonset (TGA, 5°C / min, N2) = 200°C. Tg(DSC, 5°C / min, clamped under N2) = 228°C, Tg(TMA in He, 5°C / min) = 263°C.

[0327] 1H NMR (600 MHz, DMSO-d6) 5 9.60 - 9.10 (m, 2H), 6.97 - 6.56 (m, 2H), 6.49 - 6.14 (m, 2H), 3.75 - 3.38 (m, 8H), 2.40 - 1.75 (m, 6H), 1.40 - 1.19 (m, 12H).

[0328] 13C NMR (151 MHz, DMSO-d6) 5 153.61, 153.37, 149.26, 149.07, 148.60, 148.43, 147.75, 147.43, 142.18, 142.01, 140.31, 139.92, 138.94, 138.78, 118.03, 116.35, 111.05, 109.34, 59.26, 56.84, 56.49, 42.85, 42.66, 42.41, 31.47, 31.44, 31.33, 31.28, 30.43, 30.36, 30.08.

[0329] Example 2.3: Synthesis of PHU based on Mi and 1,3-di(piperidin-4-yl)propane (PHU3).

[0330]

[0331] Scheme 5. Synthesis of PHU3 polymer.

[0332] The following amounts were used: Mi (1.175 g, 3 mmol) and 1,3-di(piperidin-4-yl)propane (0.63 g, 3 mmol). Yield: 1.44 g (79.7 %). Mn(GPC) = 94400 g moh1, Mw / Mn= 3.8, Dpn= 157. MsD(ultracentifugation) = 82500 g mol-1. Tonset (TGA, 5°C / min, on air) = 265°C; Tonset (TGA, 5°C / min, N2) = 270°C. Tg(DSC, 5°C / min, clamped under N2) = 196°C, Tg(TMA in He, 5°C / min) = 226°C.

[0333] 1H NMR (600 MHz, DMSO-d6) 5 9.39 - 9.05 (m, 2H), 6.72 (dd, J = 75.1, 15.2 Hz, 2H), 6.25 (dd, J = 30.8, 21.1 Hz, 2H), 4.24 - 3.83 (m, 4H), 2.82 (d, J = 87.9 Hz, 4H), 2.35 - 1.96 (m, 4H), 1.75 - 1.52 (m, 4H), 1.35 - 1.16 (m, 16H).

[0334] 13C NMR (151 MHz, DMSO-d6) 5 152.90, 152.79, 149.06, 148.91, 148.72, 148.63, 148.50, 147.50, 147.29, 142.06, 141.92, 139.97, 138.85, 138.74, 116.29, 110.98, 109.30, 59.26, 56.78,56.42, 56.02, 44.46, 43.99, 42.82, 42.63, 42.38, 36.08, 35.02, 31.41, 31.29, 30.38, 30.34, 30.10, 22.99.

[0335] Example 2.4: Synthesis of PHU based on Mi and octahydro-1 H-pyrrolo[3,4-b]pyridine (PHU4).

[0336]

[0337] Scheme 6. Synthesis of PHU4 polymer.

[0338] The following amounts were used: Mi (1.175 g, 3 mmol) and octahydro-1 H-pyrrolo[3,4-b]pyridine (0.378 g, 3 mmol). Yield: 1.28 g (82.4 %). Mn(GPC) = 29100 g moh1, Mw / Mn= 1.9, Dpn= 56. Tonset (TGA, 5°C / min, on air) = 235°C; Tonset (TGA, 5°C / min, N2) = 295°C. Tg(DSC, 5°C / min, clamped under N2) = 257°C, Tg(TMA in He, 5°C / min) = 262°C.

[0339] 1H NMR (600 MHz, DMSO-d6) 59.47 - 9.03 (m, 2H), 6.76 (dd, J= 98.5, 14.9 Hz, 2H), 6.43-6.14 (m, 2H), 5.01 -4.50 (m, 1H), 4.21 - 3.39 (m, 3H), 3.33 - 2.79 (m, 2H), 2.40 - 1.96 (m, 5H), 1.86 - 1.42 (m, 3H), 1.42 - 1.15 (m, 12H).

[0340] 13C NMR (151 MHz, DMSO-d6) 5 153.46, 152.87, 152.75, 149.28, 148.66, 148.55, 147.76, 147.49, 142.19, 142.05, 140.38, 140.06, 138.57, 118.04, 116.35, 111.06, 109.42, 59.26, 56.83, 56.44, 56.03, 50.91, 48.49, 42.87, 42.67, 42.64, 42.41, 35.12, 34.34, 31.43, 31.30, 30.36, 30.11, 29.01, 24.62, 23.59, 17.24.

[0341] Example 2.5: Synthesis of PHU based on Mi and 3,3’-bipiperidine (PHU5).

[0342]

[0343] Scheme 7. Synthesis of PHU5 polymer.

[0344] The following amounts were used: Mi (1.175 g, 3 mmol) and 3,3’-bipiperidine (0.504 g, 3 mmol). Yield: 1.09 g (65 %). Mn(GPC) = 41500 g moh1, Mw / Mn= 3.1, Dpn= 74. Tonset (TGA, 5°C / min, on air) = 230°C. Tg(DSC, 5°C / min, clamped under N2) = 216°C, Tg(TMA in He, 5°C / min) = 242°C.

[0345] 1H NMR (600 MHz, DMSO-d6) 59.21 (d, J = 83.4 Hz, 2H), 6.72 (dd, J = 79.6, 16.4 Hz, 2H), 6.26 (dd, J = 42.4, 20.1 Hz, 2H), 4.18- 3.65 (m, 4H), 3.07 -2.57 (m, 4H), 2.34- 1.98 (m, 4H), 1.96 -1.52 (m, 4H), 1.37 - 1.10 (m, 16H).13C NMR (151 MHz, DMSO-d6) 6152.92, 148.64, 147.54, 142.04, 139.93, 138.81, 116.25, 111.00, 109.30, 59.26, 56.77, 56.41, 42.79, 42.60, 42.35, 31.39, 31.26, 31.23, 30.39, 30.33, 30.07. Example 2.6: Synthesis of PHU based on M2 and piperazine (PHUs).

[0346]

[0347] Scheme 8. Synthesis of PHUs polymer.

[0348] The following amounts were used: M2 (1.96 g, 4.51 mmol), piperazine (0.389 g, 4.51 mmol), DMSO (3 mL). Yield: 2.55 g (96 %). Mn(GPC) = 100300 g moh1, Mw / Mn= 4.3, Dpn= 193. Tonset (TGA, 5°C / min, on air) = 200°C; Tonset (TGA, 5°C / min, N2) = 280°C. Tg(DSC, 5°C / min, clamped under N2) = 211°C, Tg(TMA in He, 5°C / min) = 259°C.

[0349] 1H NMR (600 MHz, DMSO-d6) 5 9.70 - 9.37 (m, 2H), 8.04 - 7.83 (m, 2H), 7.56 - 7.27 (m, 6H), 6.99 - 6.43 (m, 6H), 3.44 (d, J = 88.8 Hz, 8H).

[0350] 13C NMR (151 MHz, DMSO-d6) 5 152.78, 152.59, 150.63, 148.78, 148.72, 148.07, 147.98, 143.77, 143.47, 139.40, 138.42, 137.76, 137.69, 135.86, 127.89, 125.93, 122.97, 122.42, 120.51, 118.27, 116.48, 116.20, 64.23, 63.78, 63.32.

[0351] Example 2.7: Synthesis of PHU based on M2 and 1,3-di(piperidin-4-yl)propane (PHU7).

[0352]

[0353] Scheme 11. Synthesis of PHU? polymer.

[0354] The following amounts were used: M2 (1.96 g, 4.51 mmol), 1,3-di(piperidin-4-yl)propane (0.949 g, 4.51 mmol), DMSO (3 mL). Yield: 2.70 g (93 %). Mn(GPC) = 28900 g mol"1, Mw / Mn= 3.8, Dpn—45. Tonset (TGA, 5°C / min, on air) = 265°C; Tonset (TGA, 5°C / min, N2) = 265°C. Tg(DSC, 5°C / min, clamped under N2) = 194°C, Tg(TMA in He, 5°C / min) = 207°C.

[0355] 1H NMR (600 MHz, DMSO-d6) 59.31 (s, 1H), 7.90 (t, J= 9.3 Hz, 2H), 7.51 - 7.17 (m, 6H), 6.89 - 6.29 (m, 6H), 3.98 (d, J = 81.2 Hz, 4H), 3.33 (s, 2H), 2.67 (d, J = 92.9 Hz, 4H), 1.63 (s, 4H), 1.47 - 1.06 (m, 12H).13C NMR (151 MHz, DMSO-d6) 5 152.67 152.52 150.69, 148.89, 143.18, 139.39, 139.28, 138.66, 138.01, 127.81, 125.90, 122.95, 120.48, 118.11, 116.34, 116.14, 64.21, 63.76, 44.46, 44.00, 36.01, 34.93, 31.66, 31.44, 22.94.

[0356] Comparative example 1: Synthesis of PHU polymers

[0357] General method:

[0358] Polymerization was performed in a conical 3-neck flask equipped with a mechanical stirrer. Cyclic dicarbonate (3 mmol) and diamine (3 mmol) monomers were charged inside under the flow of argon followed by 2 mL of anhydrous DMSO. The mixture was heated to 50°C using oil bath and stirred at this temperature for 3 hours. Then the heating was switched off and resulting very mixture was diluted with 40 mL of THF and stirred until complete dissolution of polymer. The product was isolated by precipitation into isopropanol. It was further collected, washed with IQ- 15 mL of methanol and dried in vacuum (<0.5 mbar) at 100°C overnight.

[0359] Comparative example 1.1: Synthesis of PHU based on Mi and N1,N3-dimethylpropane-1,3- diamine (PHUs).

[0360]

[0361] Scheme 12. Synthesis of PHUs polymer.

[0362] The following amounts were used: Mi (1.175 g, 3 mmol) and N1,N3-dimethylpropane-1,3-diamine (0.306 g, 3 mmol). Yield: 1.19 g (80.3 %). Mn(GPC) = 5300 g moh1, Mw / Mn= 2.6, Dpn= 11. TonSet (TGA, 5°C / min, on air) = 175°C. Tg(DSC, 5°C / min, clamped under N2) = 103°C, Tg(TMA in He, 5°C / min) = 125°C.

[0363] 1H NMR (600 MHz, DMSO-d6) 5 9.57 - 8.93 (m, 2H), 6.93 - 6.56 (m, 2H), 6.40 - 6.12 (m, 2H), 3.52 - 3.34 (m, 2H), 3.30 - 3.15 (m, 2H), 3.08 - 2.77 (m, 6H), 2.32 - 2.01 (m, 4H), 2.02 - 1.66 (m, 2H), 1.40 - 1.15 (m, 12H).

[0364] Comparative example 1.2: Synthesis of PHU based on Mi and N1,N2-dicyclohexylethane-1,2- diamine (PHU9).

[0365]

[0366] Scheme 13. Synthesis of PHU9 polymer.

[0367] The following amounts were used: Mi (1.175 g, 3 mmol) and N1,N2-dicyclohexylethane-1,2- diamine (0.672 g, 3 mmol). Yield: 0.90 g (49 %). Mn(GPC) < 1000 g moh1.

[0368] Comparative example 1.3: Synthesis of PHU based on DGEBA-5CC and piperazine (PHU10).

[0369]

[0370] Scheme 14. Synthesis of PHU10 polymer.

[0371] The following amounts were used: DGEBA-5CC (1.285 g, 3 mmol) and piperazine (0.258 g, 3 mmol). Yield: 0.38 g (25 %). Mn(GPC) < 1000 g moh1.

[0372] TABLE 3: SYNTHESIS AND SELECTED PROPERTIES OF PHUS.

[0373] <>

[0374]

[0375] >

[0376] <

[0377] <

[0378]

[0379] Table 4. Molecular weight determination using high-speed sedimentation.

[0380]

[0381] Condition s: 25°C: r|o=O.9446 r|o=O.787. For PHII3 (1-upo) = 0.276.

Claims

1.CLAIMS1- Method for the synthesis of a polyhydroxyurethane (PHU) is characterized in that it comprises:a) providing cyclic carbonate monomers comprising two or more phenylene carbonate groups,b) providing amine monomers comprising two or more secondary amine moieties selected from alicyclic amines, alicyclic polyamines, or any mixture thereof;c) reacting the cyclic carbonate monomers with the amine monomers in the presence of a polar aprotic solvent under reaction conditions; andd) recovering a reaction product reaction which is a polyhydroxyurethane.2- The method of claim 1 is characterized in that the polyhydroxyurethane is linear, and in that the amine monomers comprise two secondary amine moieties and are selected from a cyclic diamine, a dicyclic diamine, and any mixture thereof.3- The method of claim 1 or 2 is characterized in that the cyclic carbonate monomers and the amine monomers both have a number average molecular weight (Mn) of at most 1,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC) and in that the polyhydroxyurethane recovered in step d) has a degree of polymerization (DP) of at least 45 as determined according to the method of the description; preferably a degree of polymerization ranging from 45 to 300, preferably a degree of polymerization ranging from 45 to 150.4- The method of claim 1 or 2 is characterized in that at least one of the cyclic carbonate monomers or the amine monomers has a number average molecular weight (Mn) of more than 1 ,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC) and in that the polyhydroxyurethane recovered in step d) has a degree of polymerization (DP) of at least 10 as determined according to the method of the description; preferably a degree of polymerization ranging from 10 to 50.5- The method according to any one of claims 2 to 4 is characterized in that the linear polyhydroxyurethane recovered in step d) has a number average molecular weight (Mn) of at least 25,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC).6- The method of claim 1 is characterized in that the polyhydroxyurethane is cross linked and the amine monomers comprise at least one cyclic triamine or dicyclic triamine; with preference, the cyclic carbonate monomers in the product obtained in step d) has a conversion of at least 85 % as determined by NIR and form, at 20°C to 50°C, a gel or microgel particles.7- The method according to any one of claims 1 to 6 is characterized in that the carbonate monomers comprising two or more phenylene carbonate groups are selected from bis(phenylene carbonate), phenylene dicarbonates and phenylene triscarbonate.8- The method according to claim 7 is characterized in that the carbonate monomers comprise one or more bis(phenylene carbonate) with two o-phenylene carbonate groups that are compounds of formula (2)wherein a compound of formula (2) is:wherein one or more aromatic rings of the o-phenylene carbonate groups are optionally functionalized with one or more selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more cycloaliphatic groups, one or more aromatic groups, one or more heterocyclo groups of 3 to 6 carbon atoms with one or more heteroatoms, one or more ortho-substituted phenyl groups, one or more meta-substitued phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups with one or more heteroatoms, one or more keto heteroaromatic hydrocarbon groups with one or more heteroatoms;wherein L’ is a linker between the aromatic rings of two o-phenylene carbonate groups sharing independently one or two carbon atoms with each aromatic ring of two o-phenylene carbonate groups and that is selected from a direct bond or a structure that is or comprises one or more selected from:one or more heteroatoms;one or more linear or branched aliphatic chains;one or more linear or branched alkene or polyalkene chains;one or more linear or branched heteroaliphatic chains comprising one or more heteroatoms;one or more linear or branched heteroalkene or heteropolyalkene chains comprising one or more heteroatoms;one or more linear or branched arylene or polyarylene chains;one or more linear or branched heteroaromatic or polyheteroaromatic chains comprising one or more heteroatoms;wherein the one or more heteroatoms are selected from N, S, O, and any combination thereof;wherein, when the linker comprises one or more chains; one or more carbons of the chains are optionally substituted with one or more selected from a fluorene group, one or more alkyl groups having 1 to 12 carbon atoms, one or more alkene or polyalkene groups having 1 to 12 carbon atoms, one or more hydroxy or polyhydroxy groups having 1 to 12 carbonatoms, one or more carboxylic acid groups having 1 to 12 carbon atoms; one or more ketone group, one or more cycloaliphatic groups having from 4 to 12 carbon atoms, one or more aryl groups having from 4 to 6 carbon atoms, one or more halogens groups, and any combination thereof; wherein the halogen groups are F, Cl, Br, I and any combination thereof;wherein, when the linker comprises one or more aromatic rings or heteroaromatic rings, one or more aromatic rings or heteroaromatic rings are optionally functionalized with one or more selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more cycloaliphatic groups, one or more aromatic groups, one or more heterocyclo groups of 3 to 6 carbon atoms with one or more heteroatoms, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups with one or more heteroatoms, one or more keto heteroaromatic hydrocarbon groups with one or more heteroatoms.9- The method according to claim 8 is characterized in that the linker L’ is selected such that the carbonate monomers have a number average molecular weight (Mn) of at most 1 ,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC).10- The method according to any one of claims 8 or 9 is characterized in that the carbonate monomers comprise at least one cycloaliphatic group having from 4 to 12 carbon atoms; with preference, the carbonate monomers are or comprise at least one selected from:11-The method according to claim 8 is characterized in that the linker L’ is selected such that the carbonate monomers have a number average molecular weight (Mn) ranging from more than 1000 g / mol to at most 10,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC); with preference, the polymeric linker L’ is a a polymeric chain selected from a linear or a branched chain selected from an aliphatic chain, a polyether chain, a polyester chain, a polycarbonate chain, a diene rubber chain, and an epoxy-based linear polymer chain.12- The method according to any one of claims 1 to 11 is characterized in that the amine monomers comprise alicyclic polyamines being one or more alicyclic diamines selected from piperazine, homopiperazine, diazepane, diazinane, diazacyclooctane, diazacyclononane, diazacycloundecane, diazabicycloheptane, diazaspirooctane,diazaspirononane, diazaspirodecane, diazaspiroundecane, oxadiazaspiroundecane; and any mixture thereof; with preference, one or more alicyclic diamines are selected from piperazine, homopiperazine, and any mixture thereof.13- The method according to any one of claims 1 to 12 is characterized in that the amine monomers comprise alicyclic polyamines being one or more alicyclic diamines selected from dicyclic compounds of the formula (3), (4), and any mixture thereof,wherein a compound of formula (3) is:AB (3)with A and B being each independently a nitrogen-containing cyclic structure selected from the group consisting of aziridine, aztidine, pyrrolidine, piperidine, azepane, azocane, and with A and B sharing 1 or 2 carbon atoms;wherein a compound of formula (4) is:A-L-B (4)with A and B being each independently a nitrogen-containing cyclic structure selected from the group consisting of aziridine, aztidine, pyrrolidine, piperidine, azepane, azocane; with L being a linker between A and B, selected from a direct bond or a structure that is or comprises one or more selected from:one or more heteroatoms;one or more linear or branched aliphatic chains;one or more linear or branched alkene or polyalkene chains;one or more linear or branched heteroaliphatic chains comprising one or more heteroatoms;one or more linear or branched heteroalkene or heteropolyalkene chains comprising one or more heteroatoms;one or more linear or branched arylene or polyarylene chains;one or more linear or branched heteroaromatic or polyheteroaromatic chains comprising one or more heteroatoms;wherein the one or more heteroatoms selected from N, S, O and any combination thereof; wherein, when the linker comprises one or more chains, one or more carbons of the chains are optionally substituted with one or more selected from a fluorene group, one or more alkyl groups having 1 to 12 carbon atoms, one or more alkene or polyalkene groups having 1 to 12 carbon atoms, one or more hydroxy or polyhydroxy groups having 1 to 12 carbon atoms, one or more carboxylic acid groups having 1 to 12 carbon atoms; one or more ketone group, one or more cycloaliphatic groups having from 4 to 12 carbon atoms, one or more aryl groups having from 4 to 6 carbon atoms, one or more halogens groups, andany combination thereof; wherein the halogen groups are F, Cl, Br, I and any combination thereof;wherein, when the linker comprises one or more aromatic rings or heteroaromatic rings , one or more aromatic rings or heteroaromatic rings are optionally functionalized with one or more selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more cycloaliphatic groups, one or more aromatic groups, one or more heterocyclo groups of 3 to 6 carbon atoms with one or more heteroatoms, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups with one or more heteroatoms, one or more keto heteroaromatic hydrocarbon groups with one or more heteroatoms.14- The method according to claim 13 is characterized in that one or more alicyclic diamines are selected from octahydro-1 H-pyrrolo[3,4-b]pyridine; 1,3-di(piperidin-4-yl)propane, 3,3’- bipiperidine, 2 ,2’-bipi peridine, 4,4’-bipiperidine , and any mixture thereof.15- The method according to any one of claims 13 or 14 is characterized in that the linker L is selected such that the amine monomers have a number average molecular weight (Mn) of at most 1,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC).16- The method according to any one of claims 1 to 15 is characterized in that the amine monomers comprise or are selected from piperazine, homopiperazine octahydro-1 H- pyrrolo[3,4-b]pyridine; 1,3-di(piperidin-4-yl)propane, 3,3’-bipiperidine, 2,2’-bipiperidine, 4,4’-bipiperidine , and any mixture thereof.17- The method according to claim 13 is characterized in that the linker L is selected such that the amine monomers have a number average molecular weight (Mn) ranging from more than 1000 g / mol to at most 10,000 g / mol as determined by Size exclusion chromatography (SEC) I gel permeation chromatography (GPC); with preference, the linker L is a polymeric chain selected from a linear or a branched chain selected from an aliphatic chain, a polyether chain, a polyester chain, a polycarbonate chain, a diene rubber chain, and an epoxy-based linear polymer chain.18- The method according to any one of claims 1 to 17 is characterized in that the reaction is performed in the presence of a polar aprotic solvent wherein the carbonate monomers are provided at a concentration of at least 0.50 mol / L, and / or in that the polar aprotic solvent selected from dimethyl sulfoxide, N-Methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, sulfolane, tetra hydrofuran, dichloromethane, chloroform, 1,2,3- trichloroethane, hexamethylphosphoramide, 1,2-dichlorobenzene, 1,2,4- trichlorobenzene, 1,4-dioxane, acetone, methylethyl ketone cyclohexanone and any mixture thereof.19- The method according to any one of claims 1 to 18 is characterized in that the reaction is performed at a reaction temperature ranging from 20 to 100°C and / or for a reaction time of 20 min to 12 hours.20- A polyhydroxyurethane characterized in that it is represented by one of the formulas (6) to (8)wherein:- p is an integer from 10 to 300- A and B are each independently a nitrogen-containing cyclic structure selected from the group consisting of aziridine, aztidine, pyrrolidine, piperidine, azepane, azocane; - F is a cyclic structure comprising two tertiary amines and carbon atoms,and wherein L and L’ are linkers being the same or different and each being selected from a direct bond or a structure that is or comprises one or more selected from:one or more heteroatoms;one or more linear or branched aliphatic chains;one or more linear or branched alkene or polyalkene chains;one or more linear or branched heteroaliphatic chains comprising one or more heteroatoms;one or more linear or branched heteroalkene or heteropolyalkene chains comprising one or more heteroatoms;one or more linear or branched arylene or polyarylene chains;one or more linear or branched heteroaromatic or polyheteroaromatic chains comprising one or more heteroatoms;wherein the one or more heteroatoms selected from N, S, O and any combination thereof; further wherein in formula (7), A and B share 1 or 2 carbon atoms;with preference, the polyhydroxyurethane is synthetized by the method according to any one of the claims 1 to 19.21- The polyhydroxyurethane according to claim 20 is characterized in that the polyhydroxyurethane is represented by one of the below formulas (9) to (13)wherein n is an integer from 45 to 300.

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