Patent Description:
The global polyurethane market is growing rapidly due to the increase in demand for polyurethane in several applications such as in the manufacture of rigid and flexible foams, coatings, adhesives, sealants, elastomers and consumer & personal care products etc..

Traditional polyurethanes (PU) are synthesized by the reaction of di-functional or poly-functional hydroxyl compounds (HO-R-OH or -R-(OH)n) with di-functional or poly-functional isocyanate compounds (O=C=N-R-N=C=O or -R-(N=C=O)n), optionally in the presence of catalysts. However, such currently used production methods are faced with several drawbacks.

Firstly, isocyanates are moisture sensitive, necessitating stringent precautions for transportation, handling and storage.

Next, isocyanates and their predecessor compound, i.e. phosgene are highly toxic compounds and are considered chemical irritants. Some of the isocyanates have also been classified as potential human carcinogens. Using such toxic components in the current methods of synthesizing polyurethanes is potentially dangerous as they are hazardous to human health and also detrimental to the environment. As exposure to these toxic components can cause adverse health effects, the cost of production for such methods are high as implementation of safety measures and protocols are necessary to protect workers during the manufacturing process. New governmental regulations to limit the use of toxic chemicals also compound to the challenges faced by traditional methods of PU synthesis. Despite industries being actively involved in developing alternatives, synthesizing a suitable PU remains a challenge.

<NPL> describes the synthesis of a new biobased bis(cyclic carbonate) derived from <NUM>,<NUM>-furandicarboxylic acid (FDCA) with the incorporation of CO2. <CIT> describes a water dispersion by dispersing a polyhydroxyurethane resin, manufacturing method of water dispersion, and gas barrier film using water dispersion. <NPL> describes functionalization of hydroxyl groups in segmented polyhydroxyurethane to eliminate nanophase separation. <NPL> describes non-isocyanate thermoplastic polyhydroxyurethane (PHU) elastomers which were synthesized from cyclic carbonate aminolysis using polytetramethylene oxide (PTMO) as soft segment and divinylbenzene dicyclocarbonate and three diamine chain extenders as hard segment with a range of hard-segment content. <NPL> and <NPL> describes thermoplastic polyhydroxyurethanes (PHUs) which were synthesised from cyclic carbonate aminolysis. <CIT> describes a coating composition for forming a gas barrier layer with a polyhydroxyurethane resin as a principal component, gas barrier film, and method for producing gas barrier film. <CIT> describes an aqueous polyhydroxyurethane resin dispersion containing a polyhydroxyurethane resin finely dispersed in water. <CIT> describes a gas barrier film composed of a single layer or multiple layers, at least one layer constituting the film being a layer having gas barrier properties. <NPL> describes the synthesis and properties of poly(hydroxyurethane)s. <NPL> describes polycondensation of D-mannitol-<NUM>,<NUM>:<NUM>,<NUM>-dicarbonate with diamines. <CIT> describes biscarbonate precursors, including a method for preparing them and uses. <CIT> describes a method of forming non-isocyanate based polyurethane includes providing a cyclic carbonate, an amine, and a cooperative catalyst system that has a Lewis acid and a Lewis base. <CIT> describes preparation of cyclic carbonate monomers and polymers. <NPL> describes use of Vanillin as a renewable building-block to develop a platform of <NUM> biobased compounds for polymer chemistry. <NPL> describes glycerol serving as the exclusive bio feedstock for the preparation of high purity sorbitol tricarbonate (STC) as new intermediate for poly(carbohydrate-urethane) thermosets and <NUM>% bio-based non-isocyanate polyhydroxyurethane (NIPU) coatings. <CIT> describes isocyanate group-free polyurethanes obtained by reacting hydroxyl group-free monomers with a structural element with at least two cyclic carbonate groups. <CIT> describes polyhydric alcohol cyclic carbonates are prepared by the transesterification reaction of a polyhydric alcohol of at least four carbon atoms containing at least four hydroxyl groups with a dialkyl or diaryl carbonate in the presence of a dialkyl or diaryl tin oxide catalyst. <CIT> describes water-soluble methylolated low molecular weight polyurethanes formed from polyol carbonates and amines, and a method for treating fabrics with these methylolated polyurethanes or with methylolated polyol urethanes. <NPL> describes a lanthanum heteroscorpionate complex with exceptional catalytic activity for the synthesis of cyclic carbonates from epoxides and carbon dioxide, including an important class of bis(cyclic carbonates). <CIT> describes a preparation method of discrete metal-organic nanotubes constructed based on tetraphenyl ethylene derivatives and applications thereof. Saumya <NPL> describes the use of silver complexes with bulky ligands to convert propargylic alcohols with CO<NUM> into a class of cyclic alkylidene carbonates. <CIT> describes monomers comprising at least one <NUM>-(<NUM>-oxyethylidene)-<NUM>,<NUM>-dioxolan-<NUM>-one unit and use thereof. <CIT> describes an enhanced pyrotechnic composition including an obscurant, a fuel, an oxidizer, and a nonivamide-cyclic anhydride adduct. "Synthetic Studies by the Use of Carbonates, II. An Easy Method of Preparing Cyclic Carbonates of Polyhydroxy Compounds by Transesterification with Ethylene Carbonate", <NUM> January <NUM> (<NUM>-<NUM>-<NUM>) describes transesterification reactions of polyhydroxy compounds, such as <NUM>-O-p-nitrobenzoyl-, <NUM>-O-benzylglycerols, <NUM>,<NUM>;<NUM>,<NUM>-di-O-, <NUM>,<NUM>-O-isopropylidene-p-mannitols, <NUM>,<NUM>-O-isopropylidene-a-D-glucofuranose, uridine, <NUM>,<NUM>;<NUM>,<NUM>-di-Oisopropylidene-D-mannitol, and D-mannitol, by ethylene carbonate. <NPL> describes <NUM>,<NUM>:<NUM>,<NUM>:<NUM>,<NUM>-Tricarbonates of D-glucitol, galactitol, and D-mannitol prepared by the reaction of diphenyl carbonate with the respective hexitols.

In view of the above, there is thus a need to address or at least ameliorate one of the problems described above.

In one aspect, there is provided a compound represented by general formula (Ib):
<CHM>
wherein.

In one embodiment, ring A is selected from any one of the general formulae (III) to (V):
<CHM>
<CHM>
wherein
R3a, R3b and R3c are each independently selected from the group consisting of a hydrogen, hydroxy, halogen, cyano, amino, nitro, carboxyl, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkoxy, cycloalkyl, cycloalkenyl, alkylcarbonyl and alkoxycarbonyl.

In one embodiment, Y<NUM> is selected from the group consisting of -Z-O-Z- and -Z-O-C(=O)-Z-; Y<NUM> is selected from the group consisting of -Z-O-Z- and -Z-C(=O)-O-Z-; each Z is independently selected from the group consisting of a single bond and C<NUM>-C<NUM> alkyl.

In one embodiment, the compound is selected from the following:
<CHM>.

In one aspect, there is provided a method of preparing the compound as disclosed herein, the method comprising:
converting a precursor compound represented by general formula (VI) to the compound as disclosed herein through one or more chemical reactions:
<CHM>
wherein.

In one embodiment, the precursor compound is selected from the group consisting of pyridine-<NUM>,<NUM>-dicarboxylic acid, pyridine-<NUM>,<NUM>-dicarboxylic acid and <NUM>,<NUM>-anhydroerythritol.

In one aspect, there is provided a reaction product of the reaction between one or more compounds as disclosed herein and one or more amine containing compounds, the reaction product having hydroxyl groups and urethane/carbamate linkages.

In one embodiment, the reaction product is a polymer having a repeating unit represented by general formula (VIIb) or a derivative thereof:
<CHM>
wherein.

In on embodiment, ring A is selected from any one of the general formulae (III) to (V):
<CHM>
<CHM>
wherein
R3a, R3b and R3c are each independently selected from the group consisting of a hydrogen, hydroxy, halogen, cyano, amino, nitro, carboxyl, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkoxy, cycloalkyl, cycloalkenyl, alkylcarbonyl and alkoxycarbonyl.

In one embodiment, the reaction product is selected from the following:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
or a derivative thereof.

In one embodiment, the reaction product has one or more of the following properties: number average molecular weight (Mn) in the range of <NUM>,<NUM>/mol to <NUM>,<NUM>/mol, peak molecular weight (Mp) in the range of <NUM>,<NUM>/mol to <NUM>,<NUM>/mol and the polydispersity index (PDI) is in the range of <NUM> to <NUM>, wherein the number average molecular weight, peak molecular weight and polydispersity index are determined by gel permeation chromatography using polymethyl methacrylate (PMMA) calibration.

In one aspect, there is provided a method of preparing the reaction product as disclosed herein, the method comprising:
reacting one or more compounds as disclosed herein with one or more amine containing compounds to obtain the reaction product.

In one embodiment, the amine containing compound comprises at least two amine functional groups.

In one embodiment, the amine containing compound is selected from the group consisting of furan-<NUM>,<NUM>-diyldimethanamine (FBA), xylene diamine (XDA), diaminopentane (DAP), hexamethylenediamine (HDA), ethylenediamine, diaminopropane, diaminobutane, ether diamine, polyether diamine, dimer diamine, lysine, isophorone diamine and phenylenediamine.

In one embodiment, the method is devoid of a step containing the use of isocyanates as a reactant.

In one embodiment, the method further comprises a step of functionalising one or more hydroxyl groups present in the reaction product.

In one embodiment, the method further comprises a step of grafting a polymer to one or more hydroxyl groups present in the reaction product.

In one embodiment, the method further comprises a step of grafting one or more molecular entities or polymers to one or more furan rings present in the reaction product.

In one aspect, there is provided a functionalised or grafted product obtained according to any one of the methods disclosed herein, wherein the functionalised or grafted polymer has one or more of the following properties: solubility or dispersibility in water, solubility or dispersibility in oil, photo or thermo or redox or pH response and crosslinking ability under air, photo, thermal, redox or ionic conditions.

The term "cyclic" as used herein broadly refers to a structure where one or more series of atoms are connected to form at least one ring. The term includes, but is not limited to, both saturated and unsaturated <NUM>-membered and saturated and unsaturated <NUM>-membered rings. Examples of groups having a cyclic structure include, but are not limited to, cyclopentane, cyclopentene, cyclohexane, cyclohexene and benzene. The term "cyclic" as used herein includes "heterocyclic".

The terms "alkyl", "alkenyl", "alkynyl" and "alkoxy" as used herein broadly include straight or branched hydrocarbon chains having up to <NUM> carbon atoms (i.e. C<NUM>-<NUM>), up to <NUM> carbon atoms (i.e. C<NUM>-<NUM>), up to <NUM> carbon atoms (i.e. C<NUM>-<NUM>), up to <NUM> carbon atoms (i.e. C<NUM>-<NUM>), up to <NUM> carbon atoms (i.e. C<NUM>-<NUM>) or up to <NUM> carbon atoms (i.e. C<NUM>-<NUM>). For example, the term "alkyl" includes, but is not limited to, methyl, ethyl, <NUM>-propyl, isopropyl, <NUM>-butyl, <NUM>-butyl, isobutyl, tert-butyl, amyl, <NUM>,<NUM>-dimethylpropyl, <NUM>,<NUM>-dimethylpropyl, pentyl, isopentyl, hexyl, <NUM>-methylpentyl, <NUM>-methylpentyl, <NUM>-methylpentyl, <NUM>-methylpentyl, <NUM>,<NUM>-dimethylbutyl, <NUM>,<NUM>-dimethylbutyl, <NUM>,<NUM>-dimethylbutyl, <NUM>,<NUM>-dimethylbutyl, <NUM>,<NUM>,<NUM>-trimethylpropyl, <NUM>,<NUM>,<NUM>-trimethylpropyl, <NUM>-ethylpentyl, <NUM>-ethylpentyl, heptyl, <NUM>-methylhexyl, <NUM>,<NUM>-dimethylpentyl, <NUM>,<NUM>-dimethylpentyl, <NUM>,<NUM>-dimethylpentyl, <NUM>,<NUM>-dimethylpentyl, <NUM>,<NUM>-dimethylpentyl, <NUM>,<NUM>-dimethylpentyl, <NUM>,<NUM>,<NUM>-trimethylbutyl, <NUM>,<NUM>,<NUM>-trimethylbutyl, <NUM>,<NUM>,<NUM>-trimethylbutyl, <NUM>-methylheptyl, <NUM>-methylheptyl, octyl, nonyl and decyl. For example, the term "alkenyl" includes, but is not limited to ethenyl, vinyl, allyl, <NUM>-methylvinyl, <NUM>-propenyl, <NUM>-propenyl, <NUM>-methyl-<NUM>-propenyl, <NUM>-methyl-<NUM>-propenyl, <NUM>-butenyl, <NUM>-butenyl, <NUM>-butentyl, <NUM>,<NUM>-butadienyl, <NUM>-pentenyl, <NUM>-pententyl, <NUM>-pentenyl, <NUM>-pentenyl, <NUM>,<NUM>-pentadienyl, <NUM>,<NUM>-pentadienyl, <NUM>,<NUM>-pentadienyl, <NUM>-methyl-<NUM>-butenyl, <NUM>-hexenyl, <NUM>-hexenyl, <NUM>-hexenyl, <NUM>,<NUM>-hexadienyl, <NUM>,<NUM>-hexadienyl, <NUM>-methylpentenyl, <NUM>-heptenyl, <NUM>-heptentyl, <NUM>-heptenyl, <NUM>-octenyl, <NUM>-nonenyl and <NUM>-decenyl. For example, the term "alkynyl" includes but are not limited to ethynyl, <NUM>-propynyl, <NUM>-butynyl, <NUM>-butynyl, <NUM>-methyl-<NUM>-butynyl, <NUM>-methyl-<NUM>-butynyl, <NUM>-pentynyl, <NUM>-hexynyl, methylpentynyl, <NUM>-heptynyl, <NUM>-heptynyl, <NUM>-octynyl, <NUM>-octynyl, <NUM>-nonyl and <NUM>-decynyl. For example, the term "alkoxy" includes but is not limited to methoxy, ethoxy, n-propoxy, isopropoxy and tert-butoxy.

The term "heterocyclic" as used herein broadly refers to a structure where two or more different kinds of atoms are connected to form at least one ring. For example, a heterocyclic ring may be formed by carbon atoms and at least another atom (i.e. heteroatom) selected from oxygen (O), nitrogen (N) or (NH) and sulfur (S). The term also includes, but is not limited to, saturated and unsaturated <NUM>-membered, and saturated and unsaturated <NUM>-membered rings. Examples of groups having a heterocyclic structure include, but are not limited to furan, thiophene, <NUM>-pyrrole, <NUM>-pyrrole, <NUM>-pyrroline, <NUM>-pyrroline, <NUM>-pyrroline, <NUM>-pyrazoline, <NUM>-pyrazoline, <NUM>-pyrazoline, <NUM>-imidazoline, <NUM>-imidazoline, <NUM>-imidazoline, pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, <NUM>,<NUM>,<NUM>-triazole, <NUM>,<NUM>,<NUM>-triazole, <NUM>,<NUM>,<NUM>-oxadiazole, disubstituted <NUM>,<NUM>,<NUM>-oxadiazole, <NUM>,<NUM>,<NUM>-oxadiazole, <NUM>,<NUM>,<NUM>-oxadiazole, <NUM>,<NUM>,<NUM>-thiadiazole, <NUM>,<NUM>,<NUM>-thiadiazole, <NUM>,<NUM>,<NUM>-thiadiazole, <NUM>,<NUM>,<NUM>-thiadiazole, tetrahydrofuran, tetrahydrothiophene, pyrrolidine, <NUM>,<NUM>-dioxolane, <NUM>,<NUM>-oxathiolane, <NUM>,<NUM>-oxathiolane, pyrazolidine, imidazolidine, pyridine, pyridazine, pyrimidine, pyrazine, <NUM>,<NUM>-oxazine, <NUM>,<NUM>-oxazine, <NUM>,<NUM>-oxazine, thiazine, <NUM>,<NUM>,<NUM>-triazine, <NUM>,<NUM>,<NUM>-triazine, <NUM>,<NUM>,<NUM>-triazine, <NUM>-pyran, <NUM>-pyran, <NUM>-pyrone, <NUM>-pyrone, <NUM>,<NUM>-dioxin, <NUM>-thiopyran, <NUM>-thiopyran, tetrahydropyran, thiane, piperidine, <NUM>,<NUM>-dioxane, <NUM>,<NUM>-dithiane, <NUM>,<NUM>-dithiane, <NUM>,<NUM>-dithiane, <NUM>,<NUM>,<NUM>-trithiane, piperazine, morpholine and thiomorpholine.

The term "aromatic" as used herein when referring to hydrocarbons, refers broadly to hydrocarbons having a ring-shaped or cyclic structure with delocalised electrons between carbon atoms. The term encompasses, but is not limited to, monovalent ("aryl"), divalent ("arylene") monocyclic aromatic groups having <NUM> to <NUM> atoms. Examples of such groups include, but are not limited to, benzene, furan, thiophene, pyrrole, pyrazole, imidazole, oxazole, thiazole, triazole, oxadiazole, thiadiazole, tetrazole, benzofuran, benzothiophene, benzopyrrole, benzodifuran, benzodithiophene, benzodipyrrole, pyridine, pyridazine, pyrimidine, pyrazine, <NUM>,<NUM>,<NUM>-triazine, <NUM>,<NUM>,<NUM>-triazine and <NUM>,<NUM>,<NUM>-triazine.

The term "heteroaromatic" as used herein when referring to hydrocarbons, refers broadly to aromatic hydrocarbons that have one or more carbon atoms replaced by a heteroatom. The term encompasses, but is not limited to, monovalent ("aryl"), divalent ("arylene") monocyclic, polycyclic conjugated or fused aromatic groups having <NUM> to <NUM> atoms, where <NUM> to <NUM> atoms in each aromatic ring are heteroatoms selected from oxygen (O), nitrogen (N) or (NH) and sulfur (S). Examples of such groups include, but are not limited to, furan, thiophene, pyrrole, pyrazole, imidazole, oxazole, thiazole, triazole, oxadiazole, thiadiazole, tetrazole, benzofuran, benzothiophene, benzopyrrole, benzodifuran, benzodithiophene, benzodipyrrole, pyridine, pyridazine, pyrimidine, pyrazine, <NUM>,<NUM>,<NUM>-triazine, <NUM>,<NUM>,<NUM>-triazine and <NUM>,<NUM>,<NUM>-triazine.

The term "optionally substituted" as used herein when referring to a hydrocarbon or a chemical moiety, refers to both the situation where the hydrogen atoms originally present in the hydrocarbon or the chemical moiety are not substituted and the situation where one or more hydrogen atoms originally present in the hydrocarbon or the chemical moiety are substituted/replaced with another chemical group or atom. For example, the hydrogen atom(s) originally present may be substituted/replaced with/by a hydroxy group, a halogen, a cyano group, an amino group, a nitro group, a nitroalkyl group, a nitroalkenyl, a carboxyl group, an alkyl group, alkenyl group, an alkynyl group, an alkoxy group, a haloalkyl group, a haloalkoxy group, a haloalkenyloxy group, a cycloalkyl group, a cycloalkenyl group, a thioalkyl group, thioalkoxy group, heterocycloalkyl group, a nitroalkynyl group, a nitroheterocyclyl group, an alkylamino group, a dialkylamino group, an alkenylamine group, an alkynylamino group, an acyl group, an alkenoyl group, an alkynoyl group, an acylamino group, a diacylamino group, an acyloxy group, an alkylsulfonyloxy group, a heterocycloxy group, a heterocycloamino group, a haloheterocycloalkyl group, an alkylsulfenyl group, an alkylcarbonyloxy group, an alkylthio group, an acylthio group, phosphorus-containing groups such as phosphono and phosphinyl, an aryl group, a heteroaryl group, an alkylaryl group, an alkylheteroaryl group, silicon containing groups and boron containing groups.

The term "monomer" as used herein broadly refers to a chemical entity that may be covalently linked to one or more of such entities to form a polymer.

The term "polymer" as used herein broadly refers to a chemical compound comprising a large number of repeating structural units (typically more than about <NUM>, more than about, <NUM>, more than about <NUM>, more than about <NUM>, or more than about <NUM>) and is created through a process of polymerization. The units composing the polymer are typically derived from monomers. The term also encompasses homopolymers which are made up of one type of monomer and copolymers which are made up of two or more different monomers.

The term "precursor compound" as used herein broadly refers to a compound that may be chemically and/or physically transformed to eventually reach a compound of interest. The "precursor compound" may be transformed through one or more process steps. Therefore, it will also be understood that the "precursor compound" may be a compound that immediately or directly comes before the compound of interest in a production process for the compound of interest, or comes indirectly or several steps before the compound of interest in said production process. For example, Compound A may be transformed to Compound B before being transformed to Compound C. In this example, Compound A and Compound B may both be considered as precursor compounds of Compound C. Similarly, Compound A may be considered as a precursor compound of Compound B.

The terms "bio-based" or "bio-derived" as used herein broadly refer to the quality of being derived or being originated from living organisms or once-living organisms. Such living organisms may be animal or plants. Therefore, "bio-based source" includes, but is not limited to, a biofeedstock, a plant-based source or combinations thereof. Examples of "bio-based source" include, but are not limited to, biomass such as cellulose, hemicellulose, poly-/oligo-/di-saccharides, lignin, amino acids, triglycerides, hexose, glucose, fructose and erythritol.

The term "and/or", e.g., "X and/or Y" is understood to mean either "X and Y" or "X or Y" and should be taken to provide explicit support for both meanings or for either meaning.

Further, in the description herein, the word "substantially" whenever used is understood to include, but not restricted to, "entirely" or "completely". In addition, terms such as "comprising" and "comprise" whenever used, are intended to be non-restricting descriptive language in that they broadly include elements/components recited after such terms, in addition to other components not explicitly recited. For example, when "comprising" is used, reference to a "one" feature is also intended to be a reference to "at least one" of that feature. Terms such as "consisting" and "consist", may in the appropriate context, be considered as a subset of terms such as "comprising" and "comprise". Therefore, in embodiments disclosed herein using the terms such as "comprising" and "comprise", it will be appreciated that these embodiments provide teaching for corresponding embodiments using terms such as "consisting" and "consist". Further, terms such as "about" and "approximately" whenever used, typically means a reasonable variation, for example a variation of +/- <NUM>% of the disclosed value, or a variance of <NUM>% of the disclosed value, or a variance of <NUM>% of the disclosed value, a variance of <NUM>% of the disclosed value or a variance of <NUM>% of the disclosed value.

Furthermore, in the description herein, certain values may be disclosed in a range. The values showing the end points of a range are intended to illustrate a preferred range. Whenever a range has been described, it is intended that the range covers and teaches all possible sub-ranges as well as individual numerical values within that range. That is, the end points of a range should not be interpreted as inflexible limitations. For example, a description of a range of <NUM>% to <NUM>% is intended to have specifically disclosed sub-ranges <NUM>% to <NUM>%, <NUM>% to <NUM>%, <NUM>% to <NUM>%, <NUM>% to <NUM>%, as well as individually, values within that range such as <NUM>%, <NUM>%, <NUM>%, <NUM>% and <NUM>%. The intention of the above specific disclosure is applicable to any depth/breadth of a range.

Additionally, when describing some embodiments, the disclosure may have disclosed a method and/or process as a particular sequence of steps. However, unless otherwise required, it will be appreciated that the method or process should not be limited to the particular sequence of steps disclosed. Other sequences of steps may be possible. The particular order of the steps disclosed herein should not be construed as undue limitations. Unless otherwise required, a method and/or process disclosed herein should not be limited to the steps being carried out in the order written. The sequence of steps may be varied and still remain within the scope of the disclosure.

Exemplary, non-limiting embodiments of a compound represented by general formula (Ib), a method of preparing said compound, a reaction product of the reaction between one or more said compound and one or more amine containing compounds, and a method of preparing said reaction product are disclosed hereinafter.

In various embodiments, there is provided a compound represented by general formula (Ib):
<CHM>
wherein.

In various embodiments, ring A is a <NUM>-membered heterocyclic ring having two heteroatoms or one heteroatom independently selected from the group consisting of O, N, S and NH. For example, ring A may be selected from a thiophene (e.g. disubstituted thiophene), a pyrrole (e.g. disubstituted <NUM>-pyrrole, disubstituted <NUM>-pyrrole), pyrone, an oxazole (e.g. disubstituted oxazole, disubstituted isoxazole), an isothiazole (e.g. disubstituted isothiazole), a tetrahydrofuran (e.g. disubstituted tetrahydrofuran), a tetrahydrothiophene (e.g. disubstituted tetrahydrothiophene), a pyrrolidine (e.g. disubstituted pyrrolidine) and. It will be appreciated that in various embodiments, ring A may be termed as a disubstituted ring due to it having two bonds to Y<NUM> and Y<NUM>.

In various embodiments, the <NUM>-membered heterocyclic ring is heteroaromatic. In these embodiments, ring A is selected from disubstituted thiophene, disubstituted pyrrole,, oxazole anddisubstituted isothiazole,.

In various embodiments, ring A is a <NUM>-membered heterocyclic ring having two heteroatoms or one heteroatom independently selected from the group consisting of O, N, S and NH. For example, ring A may be selected from disubstituted pyridine, disubstituted pyridazine, disubstituted pyrimidine, disubstituted pyrazine, disubstituted <NUM>,<NUM>,<NUM>-triazine, <NUM>,<NUM>,<NUM>-triazine, disubstituted <NUM>,<NUM>,<NUM>-triazine, disubstituted piperidine and disubstituted piperazine.

In various embodiments, the <NUM>-membered hydrocarbon ring A is heteroaromatic. In these embodiments, ring A is selected from disubstituted pyridine, disubstituted pyridazine, disubstituted pyrimidine, disubstituted pyrazine, disubstituted <NUM>,<NUM>,<NUM>-triazine, disubstituted <NUM>,<NUM>,<NUM>-triazine and disubstituted <NUM>,<NUM>,<NUM>-triazine.

In various embodiments, ring A is selected from the group consisting of disubstituted tetrahydrofuran and disubstituted pyridine. In various embodiments, ring A is selected from the group consisting of <NUM>,<NUM>-disubstituted pyridine, <NUM>,<NUM>-disubstituted pyridine, <NUM>,<NUM>-disubstituted pyridine, <NUM>,<NUM>-disubstituted pyridine, <NUM>,<NUM>-disubstituted pyridine, <NUM>,<NUM>-disubstituted pyridine, <NUM>,<NUM>-disubstituted tetrahydrofuran, <NUM>,<NUM>-disubstituted tetrahydrofuran, <NUM>,<NUM>-disubstituted tetrahydrofuran and <NUM>,<NUM>-disubstituted tetrahydrofuran. In some embodiments, ring A is <NUM>,<NUM>-disubstituted pyridine, <NUM>,<NUM>-disubstituted pyridine, <NUM>,<NUM>-disubstituted pyridine, <NUM>,<NUM>-disubstituted pyridine, or <NUM>,<NUM>-disubstituted tetrahydrofuran.

In various embodiments, ring A is selected from any one of the general formulae (III) to (V):
<CHM>
<CHM>
wherein
R3a, R3b and R3c are each independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an amino group, a nitro group, a carboxyl group, C<NUM>-C<NUM> alkyl group, a C<NUM>-C<NUM> alkenyl group, a C<NUM>-C<NUM> alkynyl group a C<NUM>-C<NUM> alkoxy group, a C<NUM>-C<NUM> haloalkyl group, a C<NUM>-C<NUM> haloalkoxy group, a C<NUM>-C<NUM> cycloalkyl group, a C<NUM>-C<NUM> cycloalkenyl group, a C<NUM>-C<NUM> alkylcarbonyl group and a C<NUM>-C<NUM> alkoxycarbonyl group.

In various embodiments, R3a, R3b and R3c are each a hydrogen atom.

In various embodiments, Y<NUM> is selected from the group consisting of a single bond, -Z-O-Z-, -Z-NRb-Z-, -Z-O-C(=O)-Z-, -Z-NRb-C(=O)-Z- and -Z-NRb-C(=O)-O-Z-, where Rb is H or C<NUM>-C<NUM> alkyl.

In various embodiments, Y<NUM> is selected from the group consisting of a single bond, -Z-O-Z-, -Z-NRb-Z-, -Z-C(=O)-O-Z-, -Z-C(=O)-NRb-Z- and Z-O-C(=O)-NRb-Z-, where Rb is H or C<NUM>-C<NUM> alkyl.

In various embodiments, the compound represented by general formula (Ib) comprises cyclic biscarbonate functionality. The cyclic biscarbonate may be a pyridine-based cyclic biscarbonate or a tetrahydrofuran-based cyclic biscarbonate. Advantageously, embodiments of the compound disclosed herein possessing said cyclic biscarbonate functionality make the compounds disclosed herein attractive for use as monomers in polymerization reactions.

In various embodiments, the compound represented by general formula (Ib) comprises ether, amine, ester, amide or carbamate linkages.

In various embodiments, when the compound disclosed herein is a cyclic biscarbonate comprising ether linkages, Y<NUM> and Y<NUM> are each -Z-O-Z-.

In various embodiments, when the compound disclosed herein is a cyclic biscarbonate comprising amine linkages, Y<NUM> and Y<NUM> are each -Z-NRb-Z-.

In various embodiments, when the compound disclosed herein is a cyclic biscarbonate comprising ester linkages, Y<NUM> is -Z-O-C(=O)-Z- and Y<NUM> is -Z-C(=O)-O-Z-.

In various embodiments, when the compound disclosed herein is a cyclic biscarbonate comprising amide linkages, Y<NUM> and Y<NUM> are each independently selected from the group consisting of -Z-NRb-C(=O)-Z- and -Z-C(=O)-NRb-Z-. In some embodiments, Y<NUM> is -Z-NRb-C(=O)-Z- and Y<NUM> is -Z-C(=O)-NRb-Z-.

In various embodiments, when the compound disclosed herein is a cyclic biscarbonate comprising carbamate linkages, Y<NUM> and Y<NUM> are each independently selected from the group consisting of -Z-NRb-C(=O)-O-Z- and -Z-O-C(=O)-NRb-Z-. In some embodiments, Y<NUM> is -Z-NRb-C(=O)-O-Z- and Y<NUM> is -Z-O-C(=O)-NRb-Z-.

In various embodiments, Y<NUM> and Y<NUM> are the same. As may be appreciated, when Y<NUM> and Y<NUM> are indicated to be the same, it includes the situation where Y<NUM> shares the same chemical functionality/chemical group as Y<NUM> even though the structural formula of Y<NUM> is recited in the reverse direction as that of Y<NUM>, for example,.

In some embodiments, Y<NUM> is not -(CH<NUM>)-O-C(=O)-. In some embodiments, Y<NUM> is not -C(=O)-O-(CH<NUM>)-.

In various embodiments, each Z can be the same or different and is each independently selected from the group consisting of a single bond, saturated aliphatic chain and unsaturated aliphatic chain. In various embodiments, the saturated or unsaturated aliphatic chain is unsubstituted. In various embodiments, the saturated or unsaturated aliphatic chain comprises linear, branched and/or cyclic hydrocarbon compound having from <NUM> carbon atom to <NUM> carbon atoms, or from <NUM> carbon atom to <NUM> carbon atoms. For example, the saturated aliphatic chain may be -C<NUM>-C<NUM> alkyl- or -C<NUM>-C<NUM> cycloalkyl- and the unsaturated aliphatic chain may be -C<NUM>-C<NUM> alkenyl-, -C<NUM>-C<NUM> alkynyl- or -C<NUM>-C<NUM> cycloalkenyl-. In some embodiments, the saturated or unsaturated aliphatic chain further comprises at least one substituent selected from the group consisting of O, N, S and NH. For example, the saturated aliphatic chain may be -C<NUM>-C<NUM> heteroalkyl-, -C<NUM>-C<NUM> alkylcarbonyl- or -C<NUM>-C<NUM> alkylamino- and the unsaturated aliphatic chain may be -C<NUM>-C<NUM> heteroalkenyl-, -C<NUM>-C<NUM> alkenylcarbonyl- or -C<NUM>-C<NUM> alkenylamino-. In various embodiments, one or more hydrogen atom(s) in the saturated aliphatic chain and unsaturated aliphatic chain are optionally substituted.

In various embodiments, the compound is selected from the following:
<CHM>.

In various embodiments, the aromatic units present in the compound disclosed herein are in the form of a disubstituted pyridine. Various embodiments of the compound disclosed herein do not contain or is substantially devoid of structures that resemble bisphenol A, p-terephathlic acid and vanillin-based linkers.

Various embodiments of the compound disclosed herein differ from a similar compound containing bisphenol A at least in that embodiments of compound disclosed herein does not contain
<CHM>.

Various embodiments of the compound disclosed herein differ from a similar compound containing p-terephathlic acid at least in that embodiments of compound disclosed herein does not contain
<CHM>.

In various embodiments, there is provided a method of preparing a compound represented by general formula (Ib), the method comprising:.

In various embodiments, the step of deriving a precursor compound from a bio-based source comprises subjecting the bio-based source to a variety of chemical, physical and/or biological steps/reactions/processes. In various embodiments, the chemical and/or biological reactions comprise biocatalysis, fermentation and dehydration, optionally catalysed with an acid or a base. Physical steps or processes may include milling, grinding, crushing or pulverizing.

In various embodiments, the bio-based source comprises biomass selected from plant-based polymers/molecules and sugar molecules. In some embodiments, the plant-based polymer/moleules comprises phenolic groups. In one embodiment, the plant-based polymer is cellulose, hemicellulose, and lignin. In some embodiments, the sugar molcules are selected from the group consisting of hexose, glucose, fructose and erythritol.

In various embodiments, the bio-based source is biomass feedstock.

In various embodiments, the step of deriving the precursor compound comprises deriving the precursor compound from a bio-based source selected from cellulose, hemicellulose, lignin, triglycerides, amino acids, hexose, glucose, fructose and erythritol.

In various embodiments of the method disclosed herein, the precursor compound is selected from the group consisting of pyridine-<NUM>,<NUM>-dicarboxylic acid, pyridine-<NUM>,<NUM>-dicarboxylic acid, pyridine-<NUM>-<NUM> dicarboxyllic acid and <NUM>,<NUM>-anhydroerythritol.

In various embodiments, ring A is similar to that described above.

In various embodiments, R<NUM> and R<NUM> are each independently selected from the group consisting of -OH, -C(=O)H, -C(=O)-OH, -(C<NUM>-C<NUM> alkyl)-OH and -(C<NUM>-C<NUM> alkyl)-NRcRd, where Rc and Rd are independently selected from the group consisting of H or C<NUM>-C<NUM> alkyl. In various embodiments, both Rc and Rd are H. In various embodiments, R<NUM> and R<NUM> are each independently selected from the group consisting of -OH, -C(=O)H, -C(=O)-OH, -CH<NUM>-OH and -CH<NUM>-NH<NUM>.

In various embodiments, R<NUM> and R<NUM> are the same. For example, in some embodiments, both R<NUM> and R<NUM> are each -CH<NUM>-OH. In some embodiments, both R<NUM> and R<NUM> are each -C(=O)-OH. In some embodiments, both R<NUM> and R<NUM> are each -CH<NUM>-NH<NUM>. In some embodiments, both R<NUM> and R<NUM> are each -OH.

In various embodiments, R<NUM> and R<NUM> are not the same. For example, in some embodiments, R<NUM> is -CH<NUM>-OH and R<NUM> is -C(=O)H. In some embodiments, R<NUM> is -CH<NUM>-OH and R<NUM> is -C(=O)H.

In various embodiments, the step of converting the precursor compound to the compound represented by general formula (Ib) through one or more chemical reactions comprises performing at least one of the one or more chemical reactions to form an ester, an ether, an amine, an amide, or a carbamate.

In various embodiments, the step of converting the precursor compound to the compound represented by general formula (Ib) through one or more chemical reactions comprises performing at least one of the one or more chemical reactions in the presence of a halogenated compound. The halogen in the halogenated compound may be selected from the group consisting of F, Cl, Br and I.

In various embodiments, the halogenated compound comprises a halogenating agent. The halogenating agent may be a compound added to introduce halogen atom(s) to the precursor compound. Any suitable halgenating agent that effectively add halogen atom(s) to the precursor compound may be used in embodiments of the method disclosed herein. In various embodiments, the halogenating agent (e.g. chlorinating agent) is added to convert carboxylic acid groups in the precursor compound into acid chloride groups. In these embodiments, the chlorinating agent may be selected from the group consisting of thionyl chloride, oxalyl chloride, phosphorus (V) chloride (PCl<NUM>), phosphorus (III) chloride (PCl<NUM>) and cyanuric chloride.

In various embodiments, the halogenated compound may be used to introduce a functional group. For example, the halogenated compound may be epichlorohydrin which may be used to introduce an epoxide functional group. Accordingly, in various embodiments, the halogenated compound comprises an alkylating agent. The alkylating agent may be a compound added to introduce desired aliphatic carbon chain(s) to the precursor compound. Any suitable alkylating agent that effectively add aliphatic carbon chain(s) to the precursor compound may be used in embodiments of the method disclosed herein. In various embodiments, the alkylating agent is added to convert hydroxy groups in the precursor compound into alkoxy groups. In these embodiments, the alkylating agent may be selected from the group consisting of allylbromide and epichlorohydrin.

In various embodiments, the one or more chemical reactions comprises performing at least one of the one or more chemical reactions in the presence of an alcohol after the addition of a halogenated compound. In some embodiments, the alcohol may be selected from the group consisting of glycerol carbonate and pyridinedimethanol.

In various embodiments, the one or more chemical reactions are performed in a solvent system. Any suitable solvent that effectively serves as a medium to contain the components of the mixture may be used in embodiments of the method disclosed herein. In various embodiments, the solvent is capable of substantially dissolving the components present in the composition. In some embodiments, the solvent system comprises an organic solvent. The organic solvent may be anhydrous or dry solvent. In other embodiments, the solvent system comprises aqueous solutions. In some embodiments, the solvent system is made up of solvents selected from the group consisting of dimethylformamide (DMF), tetrahydrofuran (THF), acetone, dichloromethane (DCM), acetonitrile (ACN), dimethyl sulfoxide (DMSO), γ-valerolactone (GVL), propylene carbonate (PC), dimethylcarbonate (DMC), dioxane, dioxolane, diglyme, acetone, methyl ethyl ketone (MEK), alcohols, esters, ethers, water, sodium hydroxide solution, potassium hydroxide solution and combinations thereof. In various embodiments, the solvent may be used a catalyst to catalyse one or more chemical reactions.

In various embodiments, the method of preparing a compound represented by general formula (Ib) from a precursor compound has a yield of no less than about <NUM>%, no less than about <NUM>%, no less than about <NUM>%, no less than about <NUM>%, no less than about <NUM>%, no less than about <NUM>%, no less than about <NUM>%, no less than about <NUM>%, no less than about <NUM>%, no less than about <NUM>%, or no less than about <NUM>%.

In various embodiments, the method of preparing a compound represented by general formula (Ib) is bio-based or bio-derived. Unlike conventional methods which generally use toxic precursor compounds as starting materials, embodiments of the method disclosed herein use precursor compounds derived from readily available biomass, thereby making the presently disclosed method an environmentally benign process. At the same time, utilising renewable biomass feedstock promotes resource conservation, thereby contributing to environmental sustainability.

In various embodiments, the compounds disclosed herein are capable of being used as monomers for polymerisation reactions, particularly in the synthesis of polymers containing hydroxyl groups and urethane/carbamate linkages, i.e. polyhydroxyurethanes.

In various embodiments, there is provided a reaction product of the reaction between one or more compounds represented by general formula (Ib) and one or more amine containing compounds, the reaction product having hydroxyl groups and urethane/carbamate linkages. In one embodiment, the reaction product is a polymer obtained from the polymerisation of one or more compounds represented by general formula (Ib) and one or more amine containing compounds. The reaction product may be an oligomer or a polymer.

In various embodiments, there is provided a reaction product that is a polymer having a repeating unit represented by general formula (VIIb):
<CHM>
wherein.

In various embodiments of the reaction product disclosed herein, ring A, R<NUM>, X<NUM>, X<NUM>, Y<NUM> and Y<NUM> are similar to that described above.

In various embodiments, the reaction product comprises a derivative of a polymer of Formula VIIb.

In various embodiments, the reaction product is selected from the following:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
or a derivative thereof, wherein n is an integer that is indicative of the degree of polymerization.

As may be appreciated, the present disclosure also provides a derivative of the reaction product disclosed above. For example, the derivative may be obtained from functionalising one or more of the hydroxyl groups present in the reaction product, or the derivative may be obtained from grafting a polymer to one or more of the hydroxyl groups and/or to one or more of the furan rings present in the reaction product.

In various embodiments, the derivative of the reaction product is a polymer having a backbone structure represented by a repeating unit of general formula (VIIc):
<CHM>.

In various embodiments, when the reaction product undergoes a post polymerisation functionalisation or grafting to form a derivative thereof, the derivative comprises a repeating unit that may be represented by general formula (VIId):
<CHM>
wherein M is independently selected from the group consisting of hydrogen, phosphoryl, alkyl sulfonate, amino, thiol, aminocarbonyl, aminoalkylcarbonyl, thiolcarbonyl, alkyl, alkylcarbonyl, alkenyl, alkenylcarbonyl, arylalkyl, arylalkylcarbonyl, arylalkenyl, arylalkenylcarbonyl, hydroxyl, alkylhydroxycarbonyl, polyester, polyamide, polycarbonate, polysiloxane, peptide, protein and combinations thereof.

In various embodiments, only one M is H, i.e. both M are not H at the same time.

In various embodiments, the alkyl sulfonate may be n-butyl sulfonate, polysiloxane may be selected from polydimethylsiloxane (PDMS) and the polyester may be selected from polylactide (PLA) and polycaprolactone (PCL).

In various embodiments, M is derived from a molecular entity that is capable of reacting with hydroxyl groups present in the reaction product. In some embodiments, the molecular entity is selected from the group consisting of phosphate, sultone, amino acid, peptide, protein (or their derivatives such as amino acid chloride hydrochloride), fatty acid and carboxylic acid (or their derivatives such as fatty acid anhydride and fatty acid chloride). In other embodiments, the molecular entity is selected from the group consisting of polysiloxane (such as polydimethylsiloxane), cyclic amides (such as lactams), cyclic carbonates and cyclic esters. The cyclic esters may be selected from the group consisting of lactide and lactone (such as propiolactone, butyrolactone, and caprolactone).

In various embodiments, a molecular entity selected from tetra-n-butylammonium dihydrogen phosphate, <NUM>,<NUM>-butane sultone, glycine chloride hydrochloride, D-phenylalanine chloride hydrochloride, N-acetyl cysteine chloride, butyric acid anhydride, palmitic acid chloride, cinnamic acid chloride, oleic acid chloride, linoleic acid chloride may be used for the functionalisation of the -OH groups of the reaction product, i.e. converting a reaction product having -OH groups to a derivative having -OM groups. In various embodiments, a molecular entity selected from hydroxylated/oxalylated polydimethylsiloxane, lactide and caprolactone may be used for grafting to the -OH groups of the reaction product, i.e. converting a reaction product having -OH groups to a graft polymer having -OM groups. In various embodiments, the graft polymer is represented by the formula: PHU-g-OM.

In various embodiments, X<NUM>, R<NUM>, X<NUM>, Y<NUM>, ring A and Y<NUM> in the formulae VIIc and VIId are similar to that described above.

In various embodiments, the derivative of the reaction product is represented by the formula: PHU-g-P, where P is one or more of molecular entity, a monomer, a oligomer, a polymer, peptide or protein.

In various embodiments, one or more molecular entities or polymers containing maleimide end groups may be used for grafting to one or more furan rings present in the reaction product, i.e. converting a reaction product having one or more furan group(s) to a graft polymer having one or more Diels-Alder adduct(s) that resembles the following structure:
<CHM>
For example, the derivative may be obtained from grafting a polymer containing maleimide end groups to one or more furan rings present at X<NUM> and/or ring A of the reaction product as disclosed herein.

In various embodiments, the reaction product has a number average molecular weight (Mn) in the range of from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, or about <NUM>,<NUM>/mol. In some embodiments, the number average molecular weight of the reaction product is about <NUM>,<NUM>/mol, about <NUM>,<NUM>/mol, about <NUM>,<NUM>/mol, about <NUM>,<NUM>/mol, about <NUM>,<NUM>/mol, about <NUM>,<NUM>/mol, about <NUM>,<NUM>/mol, about <NUM>,<NUM>/mol, about <NUM>,<NUM>/mol or about <NUM>,<NUM>/mol.

In various embodiments, the reaction product has a peak molecular weight (Mp) in the range of from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, or about <NUM>,<NUM>/mol. In some embodiments, the peak molecular weight of the reaction product is about <NUM>,<NUM>/mol, about <NUM>,<NUM>/mol, about <NUM>,<NUM>/mol, about <NUM>,<NUM>/mol, about <NUM>,<NUM>/mol, about <NUM>,<NUM>/mol, about <NUM>,<NUM>/mol, about <NUM>,<NUM>/mol, about <NUM>,<NUM>/mol or about <NUM>,<NUM>/mol.

In various embodiments, the reaction product has a polydispersity index (PDI) in the range of from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM> or about <NUM>.

In various embodiments, the number average molecular weight, peak molecular weight and polydispersity index are determined by gel permeation chromatography using polymethyl methacrylate (PMMA) calibration.

Embodiments of the reaction product represented by general formula(VIIb) disclosed herein are structurally different from traditional polyurethanes at least in that embodiments of the reaction product disclosed herein contain hydroxyl groups. In various embodiments, the reaction products disclosed herein are non-isocyanate polyhydroxyl-urethanes (NIPUs/PHUs) comprising free secondary or primary hydroxyl functional groups in their structure in addition to the carbamate linkages. In various embodiments, the reaction products are hydrophilic. Without being bound by theory, it is believed that the hydroxyl groups present within the reaction product increase the adhesion properties and can be further functionalized or cross-linked. Without being bound by theory, it is also believed that hydrogen bonds will increase the thermal and hydrolytic stability as well as chemical resistance to non-polar solvents.

As compared to known polyurethanes, embodiments of the reaction product disclosed herein have higher degradation temperature and higher chemical stability to hydrolysis. As compared to known polyurethanes, embodiments of the reaction product disclosed herein also have better adhesion properties and can be further functionalized/cross-linked for use in a wide array of applications.

In various embodiments, there is provided a method of preparing the reaction product disclosed herein, the method comprising: reacting one or more compounds represented by general formula (Ia) and/or (Ib) with one or more amine containing compounds to obtain the reaction product.

In various embodiments of the method disclosed herein, the one or more amine containing compound comprises at least two amine functional groups. In various embodiments, the amine containing compound is an aliphatic diamine or an aromatic diamine. The amine containing compound may comprise two, three, four, five, six, seven or eight amine functional groups.

In various embodiments of the method disclosed herein, the amine containing compound comprises a bio-based amine. The bio-based amine is derived from natural resources selected from the group consisting of isosorbide-based diamine, vanillin-based diamine, grapeseed oil-based polyamine, fatty acid based diamine, pentaerythritol-based triamine.

In various embodiments of the method disclosed herein, the amine containing compound is selected from the group consisting of furan-<NUM>,<NUM>-diyldimethanamine (FBA), xylene diamine (XDA), diaminopentane (DAP), hexamethylenediamine (HDA), isophorone diamine, ether diamine, polyether diamine, dimer diamine and lysine.

In various embodiments, the method of preparing a compound represented by general formula (Ib) and the method of preparing a reaction product represented by general formula (VIIb) disclosed herein are devoid of a step containing the use of isocyanates as a reactant.

In various embodiments, the methods disclosed herein are advantageous over existing technologies at least in that the aromatic and aliphatic cyclic biscarbonate monomers and polyhydroxyurethanes produced from the polymerisation of said monomers are bio-based/bio-derived. In various embodiments of the method disclosed herein, the amine precursors used for the preparation of the reaction product are derived from a bio-based source. In various embodiments therefore, the reaction products disclosed herein are innocuous biocompatible polymers, making them attractive as alternative sustainable materials for future applications such as in coatings, additives, adhesives, film formers, pigment dispersing agents and oil thickeners.

In various embodiments, the methods disclosed herein is less toxic, relatively safer and more environmentally friendly than the method described in Scheme <NUM> below.

In various embodiments, the method of preparing a reaction product represented by general formula (Vllb) has a monomer conversion % of no less than about <NUM>%, no less than about <NUM>%, no less than about <NUM>%, no less than about <NUM>%, no less than about <NUM>%, no less than about <NUM>%, no less than about <NUM>%, no less than about <NUM>%, no less than about <NUM>%, or no less than about <NUM>%.

In various embodiments, the method further comprises a step of functionalising the hydroxyl groups present in the reaction product. In various embodiments, the step of functionalising the hydroxyl groups comprises a step whereby the hydroxyl groups are phosphorylated by a phosphate, a step whereby the hydroxyl groups are sulfonated by a sultone or a step where the hydroxyl groups undergo esterification with amino acids, peptides, proteins, (or their derivatives such as amino acid chloride hydrochloride), carboxylic acids (or their derivatives such as acid chloride or anhydride) fatty acids, (or their derivatives such as fatty acids chloride or fatty acids anhydride).

In various embodiments, the method further comprises a step of grafting a polymer from the hydroxyl groups present in the reaction product to obtain a graft polymer. In various embodiments, the step of grafting comprises ring opening polymerisation of cyclic amides (such as lactams), cyclic carbonates and cyclic esters. The cyclic esters may be selected from the group consisting of lactide and lactone (such as propiolactone, butyrolactone, and caprolactone). In various embodiments, the step of grafting comprises grafting polysiloxane (such as hydroxylated/oxalylated polydimethylsiloxane) to the -OH groups present in the reaction product.

In various embodiments, the method further comprises a step of grafting a polymer containing maleimide end group(s) to the furan rings present in the reaction product to obtain a graft polymer. In various embodiments, the step of grafting comprises Diels-Alder reaction(s) between the maleimide end group(s) of the polymer and the furan ring(s) of the reaction product. The furan ring(s) may be present at X<NUM> and/or ring A of the reaction product.

In various embodiments, the method further comprises a step of functionalising one or more hydroxyl groups present in the reaction product disclosed herein or polyhydroxyurethanes that are obtained through the reaction between one or more bis/multi-carbonates and an amine containing compound.

In various embodiments, the method further comprises a step of grafting a polymer to one or more hydroxyl groups present in the reaction product disclosed herein or polyhydroxyurethanes that are obtained through the reaction between one or more bis/multi-carbonates and an amine containing compound.

In various embodiments, the functionalised or grafted polymer has one or more of the following properties: solubility or dispersibility in water, solubility or dispersibility in oil, photo or thermo or redox or pH response and crosslinking ability under air, photo, thermal or ionic conditions.

Example embodiments of the disclosure will be better understood and readily apparent to one of ordinary skill in the art from the following examples, tables and if applicable, in conjunction with the figures.

The examples describe a method of preparing a compound and a method of preparing a reaction product of said compound from a bio-based source in an environmentally benign process in accordance with various embodiments of the present disclosure. Broadly, the general concept of methods disclosed herein may be illustrated in <FIG>, <FIG> and <FIG> as follows.

Referring to <FIG>, it can be seen that a reaction product represented by general formula (VIIb) and/or (VIIc) and/or (VIId) and/or PHU-g-P (for example, any one of polymers (<NUM>)-(<NUM>) or a derivative thereof described herein) may be prepared from a compound represented by general formula (Ib) (for example any one of PBC, PBC-<NUM> and HFBC described herein) which in turn may be optionally derived from a bio-based source (for example, lignin, hexose, glucose and erythriol disclosed herein).

Referring now to <FIG>, there is shown a schematic flowchart <NUM> for illustrating a method of preparing a compound represented by general formula (Ib) (for example any one of PBC, PBC-<NUM> and HFBC described herein). At step <NUM>, a precursor compound represented by general formula (VI) (for example any one of pyridine-<NUM>,<NUM>-dicarboxylic acid, pyridine-<NUM>,<NUM>-dicarboxylic acid and <NUM>,<NUM>-anhydroerythritol described herein), optionally derived from a bio-based source. At step <NUM>, the method further comprises converting the precursor to said compound through one or more chemical reactions, wherein at least one of the one or more chemical reactions is carried out in the presence of a halogenated compound. At step <NUM>, the method further comprises reducing or oxidising the precursor compound prior to undergoing one or more chemical reactions in the presence of a halogenated compound (i.e. a compound containing a halogen such as but not limited to thionyl chloride, epichlorohydrin allylbromide). As will be appreciated, the choice of the halogenated compound may varied depending on the identity of the precursor compound. The dotted lines of the boxes containing steps <NUM> and <NUM> indicate that these steps may be absent in some embodiments of the present disclosure depending on factors such as which part of a broader process the method pertains to and/or the identity of the bio-based source and/or the identity of the precursor compound desired.

Turning to <FIG>, there is shown a schematic flowchart <NUM> for illustrating a method of preparing a reaction product in the form of a polymer represented by general formula (VIIb) and/or (VIIc) and/or (VIId) and/or PHU-g-P in accordance with various embodiments disclosed herein. At step <NUM>, one or more compounds in the form of a first monomer type represented by general formula (Ib) are provided. At step <NUM>, one or more amine containing compounds in the form of a second monomer type are provided. At step <NUM>, the first and second monomer types are reacted to obtain a polymer represented by general formula (VIIb).

In addition, the following examples further show that embodiments of the presently disclosed method provide a green and sustainable strategy to produce cyclic biscarbonates and polyhydroxyurethanes as use of toxic isocyanates and phosgene may be avoided.

As will be shown in the following examples, embodiments of the presently disclosed method synthesize new aliphatic and aromatic cyclic biscarbonates and new polyhydroxyurethanes that are capable of addressing several problems of conventional methods used in the art. The polyhydroxyurethanes disclosed herein are innocuous biocompatible polymers, making them attractive as greener, safer, bio-renewable and sustainable materials for a wide array of applications. It should be appreciated that the examples provided below are meant to be merely illustrative and not in any way meant to be exhaustive or restrictive.

Several biscarbonate monomers have been developed from bio-based platform chemicals such as <NUM>,<NUM>-anhydroerythritol, pyridine dicarboxylic acid and glycerol. Renewable C-<NUM> feedstock such as CO<NUM> was also utilized towards creating cyclic carbonate structures. The synthesis protocols for the monomers and the polyhydroxy urethane polymers are summarized in Schemes <NUM> and <NUM>, and explained below. <CHM>
<CHM>
<CHM>.

Furan based cyclic biscarbonate with ester linkage was synthesized from FDCA by a one pot esterification with glycerol carbonate as shown in Scheme <NUM>.

To a round bottom flask connected with condenser, FDCA (<NUM> mmol, <NUM>), SOCl<NUM> (<NUM> mmol, <NUM>) and <NUM> of dimethylformamide (DMF) were added and the reaction was carried out at <NUM> under argon for <NUM>. The reaction mixture was then cooled down to room temperature. Et<NUM>N (<NUM> mmol, <NUM>) and glycerol carbonate (<NUM> mmol, <NUM> in <NUM> of dry THF) were added slowly and the mixture was further heated to <NUM> overnight. After the reaction, the excess amount of Et<NUM>N, SOCl<NUM> and DMF were removed under high vacuum. The product was isolated as a white solid, filtered and washed with water (<NUM>, <NUM> times) and with Et<NUM>O (<NUM>, <NUM> times) to give <NUM> (<NUM> mmol) of pure bis((<NUM>-oxo-<NUM>,<NUM>-dioxolan-<NUM>-yl)methyl)furan-<NUM>,<NUM>-dicarboxylate (<NUM>%) which was characterized by <NUM>H, <NUM>C-NMR and HRMS. <NUM>H-NMR (DMSO, <NUM>): <NUM> (s, <NUM>), <NUM> (m, <NUM>), <NUM> (m, <NUM>), <NUM> (dd, J = <NUM>, <NUM>, <NUM>). <NUM>C NMR (DMSO, <NUM>): δ= <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>. HRMS (ESI) (M+H)+ m/z Calcd. For C<NUM>H<NUM>O<NUM>: <NUM>. Found: <NUM>.

The novel cyclic biscarbonate <NUM>,<NUM>'-(((furan-<NUM>,<NUM>-diylbis(methylene))-bis(oxy))bis(methylene)) bis(<NUM>,<NUM>-dioxolan-<NUM>-one), FBC-<NUM>, was synthesized by using a two-step protocol in multi gram scale starting from FDM as shown in Scheme <NUM>.

In the first step, a solution of furandimethanol (FDM) (<NUM> mmol, <NUM>), epichlorohydrin (<NUM> mmol, <NUM>) and tetrabutylammonium bromide (TBAB) (<NUM> mol%, <NUM>) in THF (<NUM>) was added into aqueous NaOH (<NUM> in <NUM>). This mixture was heated and stirred at <NUM> for <NUM>. After the reaction, the reaction mixture was diluted with <NUM> of water and the product was extracted into EtOAc (<NUM>, <NUM> times) and the combined organic layers were dried over MgSO<NUM>. After evaporation of the solvent and column chromatography of the crude reaction mixture, the diepoxy product <NUM>,<NUM>-bis((oxiran-<NUM>-ylmethoxy)-methyl)furan was isolated in <NUM> (<NUM> mmol), <NUM>% (yellow oil) and characterized by NMR and HRMS as follows. <NUM>H-NMR (CDCl<NUM>, <NUM>): <NUM> (s, <NUM>), <NUM> (q, J = <NUM>, <NUM>), <NUM> (dd, J = <NUM>, <NUM>, <NUM>), <NUM> (dd, J = <NUM>, <NUM>, <NUM>), <NUM> (m, <NUM>), <NUM> (dd, J = <NUM>, <NUM>, <NUM>), <NUM> (dd, J = <NUM>, <NUM>, <NUM>). <NUM>C NMR (CDCl<NUM>, <NUM>): δ= <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>. HRMS (ESI) (M+H)+ m/z Calcd. For C<NUM>H<NUM>O<NUM>: <NUM>. Found: <NUM>.

In the second step, the diepoxy product <NUM>,<NUM>-bis((oxiran-<NUM>-ylmethoxy)-methyl)furan (<NUM> mmol, <NUM>), tetrabutyl ammonium iodide (TBAI) (<NUM> mol%, <NUM> mmol) and pyridinedimethanol (<NUM> mol%, <NUM> mmol) were dissolved in <NUM> of dry THF, transferred into a Parr reactor and pressurized with CO<NUM> up to <NUM> psig after purging with N<NUM> followed by CO<NUM>. The reaction was carried out under stirring at <NUM> for <NUM>. After the reaction, the reactor was cooled to room temperature and depressurized. The reaction mixture was collected, the solvent evaporated and the product was purified by column chromatography. The bicarbonate product <NUM>,<NUM>'-(((furan-<NUM>,5diylbis(methylene))bis(oxy))-bis(methylene))bis(<NUM>,<NUM>-dioxolan-<NUM>-one) was isolated as a white solid (<NUM>, <NUM> mmol, <NUM>% yield) and characterized by <NUM>H, <NUM>C-NMR and HRMS as follows. <NUM>H-NMR (CDCl<NUM>, <NUM>): <NUM> (s, <NUM>), <NUM> (m, <NUM>), <NUM> (m, <NUM>), <NUM> (dd, J = <NUM>, <NUM>, <NUM>), <NUM> (ddd, J = <NUM>, <NUM>, <NUM>, <NUM>), <NUM> (dd, J = <NUM>, <NUM>, <NUM>). <NUM>C NMR (CDCl<NUM>, <NUM>): δ= <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>. HR-MS (ESI) (M+Na)+ m/z Calcd. for C<NUM>H<NUM>O<NUM>Na: <NUM>. Found: <NUM>.

Bioderived aliphatic cyclic diols such as <NUM>,<NUM>-anhydroerythritol can be another class of linkers to form aliphatic cyclic biscarbonates with tetrahydrofuran backbone. An aliphatic bio-based cyclic biscarbonate <NUM>,<NUM>'-(((tetrahydrofuran-<NUM>,<NUM>-diyl)bis(oxy))bis(methylene))bis(<NUM>,<NUM>-dioxolan-2one) was synthesized from <NUM>,<NUM>-anhydroerythritol, which was derived from the bio-feedstock erythritol. The synthetic protocol for converting <NUM>,<NUM>-anhydroerythritol to <NUM>,<NUM>'-(((tetrahydrofuran3,<NUM>-diyl)bis(oxy))bis(methylene))-bis(<NUM>,<NUM>-dioxolan-<NUM>-one) is shown in Scheme <NUM>.

<NUM>,<NUM>-anhydroerithritol (<NUM> mmol, <NUM>) was added into a mixture of KOH/THF (<NUM> mmol (<NUM>)/<NUM>). Allylbromide (<NUM> mmol, <NUM>) was added slowly into the mixture. This mixture was heated and stirred at <NUM> (under refluxing) for <NUM>. After reaction, the crude reaction mixture was diluted with water (<NUM>) and extracted with EtOAc (<NUM>, <NUM> times). The combined organic layers were then dried using MgSO<NUM>, solvent evaporated and the product <NUM>,<NUM>-bis(allyloxy)tetrahydrofuran was isolated by column chromatography in <NUM>, <NUM> mmol (<NUM>%) as an yellow oil and characterized by <NUM>H-NMR, <NUM>C-NMR and HRMS. <NUM>H-NMR (CDCl<NUM>, <NUM>): <NUM> - <NUM> (m, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> (m, <NUM>), <NUM> (m, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> (m, <NUM>). <NUM>C NMR (CDCl<NUM>, <NUM>): δ= <NUM>, <NUM>, <NUM>, <NUM>, <NUM>. HR-MS (ESI) (M+H)+ m/z Calcd. for C<NUM>H<NUM>O<NUM>: <NUM>. Found: <NUM>.

In the second step, a solution of <NUM>,<NUM>-bis(allyloxy)tetrahydrofuran (<NUM> mol, <NUM>) in dichloromethane (<NUM>) was cooled down to <NUM> followed by the addition of m-chloroperoxybenzoic acid (<NUM> mmol, <NUM>) under stirring. The reaction mixture was allowed to stir and the temperature was slowly brought to room temperature (<NUM>) during <NUM>. Another portion of m-chloroperoxybenzoic acid (<NUM> mmol) was added into the reaction mixture and the reaction mixture refluxed overnight. The reaction was cooled down to room temperature, <NUM> of water was added and the crude mixture was extracted with EtOAc (<NUM>, <NUM> times). The combined organic layers were dried over MgSO<NUM>, solvent evaporated and the product <NUM>,<NUM>-bis(oxiran-<NUM>-ylmethoxy)tetrahydrofuran was isolated as a diastereomeric mixture by column chromatography to yield <NUM>, <NUM> mmol (<NUM>%) of product as a colourless oil and was characterized by <NUM>H NMR, <NUM>C-NMR and HRMS. <NUM>H-NMR (CDCl<NUM>, <NUM>): <NUM>-<NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>), <NUM> (ddd, J = <NUM>, <NUM>, <NUM>, <NUM>), <NUM> (ddq, J = <NUM>, <NUM>, <NUM>, <NUM>), <NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>). <NUM>C NMR (CDCl<NUM>, <NUM>): δ= <NUM>-<NUM>, <NUM>-<NUM>, <NUM>-<NUM>, <NUM>-<NUM>, <NUM>- <NUM>. HR-MS (ESI) (M+NH<NUM>)+ m/z Calcd. for C<NUM>H<NUM>NO<NUM>: <NUM> Found: <NUM>.

In the third step, <NUM>,<NUM>-bis(oxiran-<NUM>-ylmethoxy)tetrahydrofuran (<NUM> mmol, <NUM>), tetrabutyl ammonium iodide (<NUM> mol%, <NUM>) and pyridine-<NUM>,<NUM>-diyldimethanol (<NUM> mol%, <NUM>) were dissolved in <NUM> dry THF in a Parr reactor and pressurized with CO<NUM> (up to <NUM> psi) after purging with N<NUM> followed by CO<NUM>. This mixture was heated at <NUM> under stirring for <NUM>. After reaction, the Parr reactor was cooled down to room temperature and depressurized. The reaction mixture was collected, the solvent evaporated and the product <NUM>,<NUM>'-(((tetrahydrofuran-<NUM>,<NUM>-diyl)bis(oxy))bis(methylene))-bis(<NUM>,<NUM>-dioxolan-<NUM>-one) was isolated as a diastereomeric mixture by column chromatography in <NUM>, (<NUM> mmol, <NUM>% yield) as an yellow oil and characterized by <NUM>H, <NUM>C-NMRs and MS. <NUM>H-NMR (CDCl<NUM>, <NUM>): <NUM> (m, <NUM>), <NUM> (m, <NUM>), <NUM> (m, <NUM>), <NUM> (m, <NUM>), <NUM> (m, <NUM>), <NUM>-<NUM> (m, <NUM>). <NUM>C NMR (CDCl<NUM>, <NUM>): δ= <NUM>-<NUM>, <NUM>-<NUM>, <NUM>-<NUM>, <NUM>-<NUM>, <NUM>-<NUM>, <NUM>-<NUM>. HR-MS (ESI) (M+H)+ m/z Calcd. for C<NUM>H<NUM>O<NUM>: <NUM>. Found: <NUM>.

Pyridine containing cyclic biscarbonate with ester linkage can be synthesized from pyridine containing dicarboxylic acids or esters with glycerol carbonate via standard esterification by or transesterification protocols e.g. catalytic esterification/transesterification or by using coupling agents. Pyridine containing cyclic carbonates with ether linkages can be synthesized from corresponding furan containing diols via alkylations using a cyclic carbonate containing halide or pseudo halide or epoxide containing halide or pseudo halide followed by CO<NUM> insertion.

The synthetic protocol for converting pyridine-<NUM>,<NUM>-dicarboxylic acid to bis((<NUM>-oxo-<NUM>,<NUM>-dioxolan4-yl)methyl)-pyridine-<NUM>,<NUM>-dicarboxylate is shown in Scheme <NUM>.

To a round bottom flask connected with condenser, pyridine-<NUM>,<NUM>-dicarboxylic acid (<NUM> mmol, <NUM>), SOCl<NUM> (<NUM> mmol, <NUM>) and <NUM> of DMF were added and the reaction was carried out at <NUM> under argon for <NUM>. The reaction mixture was then cooled down to room temperature, Et<NUM>N (<NUM> equiv. , <NUM>) and glycerol carbonate (<NUM> mmol, <NUM> in <NUM> of THF) were added slowly and was further heated at <NUM> overnight. After the reaction, the excess amount of Et<NUM>N, SOCl<NUM> and solvent were removed under vacuum. The product bis((<NUM>-oxo-<NUM>,<NUM>-dioxolan-<NUM>-yl)methyl)pyridine-<NUM>,<NUM>-dicarboxylate was isolated as a white solid, filtered and washed with water (<NUM>, <NUM> times) and with Et<NUM>O (<NUM>, <NUM> times) to give <NUM> (<NUM> mmol) of pure product (<NUM>%) which was characterized by H, <NUM>C-NMR and HRMS. <NUM>H-NMR (CDCl<NUM>, <NUM>): <NUM> (dd, J = <NUM>, <NUM>, <NUM>), <NUM> (dd, J = <NUM>, <NUM>, <NUM>), <NUM> (dd, J = <NUM>, <NUM>, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> - <NUM> (m, <NUM>). <NUM>C NMR (CDCl<NUM>, <NUM>): δ= <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>. HR-MS (ESI) (M+H)+ m/z Calcd. for C<NUM>H<NUM>NO<NUM>: <NUM>. Found: <NUM>.

Preparation of FDCA chloride in THF solution: To a round bottom flask connected with condenser, <NUM>,<NUM>-furandicarboxylic acid (FDCA) (<NUM>, <NUM> mmol), thionyl chloride (SOCl<NUM>) (<NUM>, <NUM> mmol) and catalytic amount of DMF (<NUM>) were added and the reaction was carried out at <NUM> under argon for <NUM>. Excess of SOCl<NUM> were removed under vacuum. Then the residue solid was redissolved in <NUM> anhydrous THF.

To a solution of trimethylamine (Et<NUM>N) (<NUM> mmol, <NUM>) and glycerol carbonate (<NUM>, <NUM> mmol) in <NUM> of anhydrous THF were added slowly to the FDCA chloride in THF solution (<NUM>) at <NUM>. After stirring at room temperature for <NUM>, the reaction was further heated to <NUM> for <NUM>. The reaction was quenched by addition of water (<NUM>). The product bis((<NUM>-oxo-<NUM>,<NUM>-dioxolan-<NUM>-yl)methyl)furan-<NUM>,<NUM>-dicarboxylate was precipitated out as a white solid. The solid was filtered and washed with water (<NUM>*<NUM>) and with THF (<NUM>*<NUM>) to give FBC-<NUM> in <NUM> (<NUM> mmol, <NUM>% yield) which was characterized by <NUM>H, <NUM>C-NMR and HRMS.

<NUM>H-NMR (DMSO, <NUM>): <NUM> (s, <NUM>), <NUM> (m, <NUM>), <NUM> (m, <NUM>), <NUM> (dd, J = <NUM>, <NUM>, <NUM>). <NUM>C NMR (DMSO, <NUM>): δ= <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>. HRMS (ESI) (M+H)+m/z Calcd. For C<NUM>H<NUM>O<NUM>: <NUM>. Found: <NUM>.

The scale up and optimized synthesis of cyclic biscarbonate <NUM>,<NUM>'-(((furan-<NUM>,<NUM>-diylbis(methylene))bis(oxy))bis(methylene))bis(<NUM>,<NUM>-dioxolan-<NUM>-one), FBC-<NUM>, is shown in Scheme <NUM>. The yield of the first step di-alkylation was increased by changing the phase transfer catalyst from tetrabutylammonium bromide to tetrabutylammonium hydrogen sulfate (TBHS). In addition, the reaction was carried out at room temperature.

To a solution of sodium hydroxide solution (<NUM>:<NUM> w/w) was added with furandimethanol (FDM) (<NUM>, <NUM> mmol) and <NUM> mol% of tetrabutylammonium hydrogen sulfate (<NUM>, <NUM> mmol). The reaction mixture was cooled to <NUM>, epichlorohydrin (<NUM>, <NUM> mmol) was added dropwise over <NUM>. The mixture was stirred at room temperature for <NUM>. The reaction was quenched by addition of water (<NUM>). The aqueous layer was extracted with pentane (<NUM>) to remove excess epichlorohydrin. Then the aqueous layer was extracted with EtOAc (<NUM>*<NUM>). The combined EtOAc extracts were washed with water (<NUM>) and were allowed to pass through a short pad of silica gel. The solvent was evaporated to obtain a pure yellow oil diepoxy product <NUM>,<NUM>-bis((oxiran-<NUM>-ylmethoxy)methyl)furan in <NUM> (<NUM> mmol, <NUM>% yield) and characterized by <NUM>H and <NUM>C NMR.

In the second step, the diepoxy product <NUM>,<NUM>-bis((oxiran-<NUM>-ylmethoxy)methyl)furan (<NUM>, <NUM> mmol), tetrabutyl ammonium iodide (TBAI) (<NUM>, <NUM> mmol, <NUM> mol%) and pyridinedimethanol (<NUM>, <NUM> mmol, <NUM> mol%) were dissolved in <NUM> of anhydrous THF, transferred into a Parr reactor and pressurized with CO<NUM> up to <NUM> psig after purging with N<NUM> followed by CO<NUM>. The reaction was carried out under stirring at <NUM> for <NUM>. After the reaction, the reactor was cooled to room temperature and depressurized. The solvent THF was removed and the mixture was redissolved in <NUM> of EtOAc. The organic layer was washed with sodium thiosulfate (<NUM>*<NUM>) to remove the iodine followed by brine (<NUM>*<NUM>). The organic layer was separated and dried by sodium sulfate. Then the volume of EtOAc was reduced to <NUM> and a white solid was precipitated out. The solid was filtered, collected and washed with pentane (<NUM>*<NUM>). The solid was dried in an oven under vacuum at <NUM> for <NUM>. The bicarbonate product <NUM>,<NUM>'-(((furan-<NUM>,<NUM>-diylbis(methylene))bis(oxy))-bis(methylene))bis(<NUM>,<NUM>-dioxolan-<NUM>-one) was isolated as a white solid (<NUM>, <NUM> mmol, <NUM>% yield) and characterized by <NUM>H NMR.

To a solution of sodium hydroxide in water (<NUM> in <NUM>), furan-<NUM>,<NUM>-diyldimethanol (<NUM>, <NUM> mmol), and tetrabutylammonium hydrogen sulfate (<NUM>, <NUM> mmol) was added and the mixture was cooled to <NUM> followed by addition of epichlorohydrin (<NUM>, <NUM> mmol) dropwise over <NUM>. The mixture was then stirred at room temperature for <NUM>. Deionised water (<NUM>) was added and the mixture was extracted with ethyl acetate (3x60 mL). The extracts were passed through a pad of silica gel using ethyl acetate : petroleum ether (<NUM> : <NUM>) as eluent and concentrated under reduced pressure. Product was obtained as a yellow liquid (<NUM>, <NUM>%).

<NUM>,<NUM>-bis((oxiran-<NUM>-ylmethoxy)methyl)furan (<NUM>, <NUM> mmol) and tetrabutylammonium bromide (TBABr) (<NUM>, <NUM> mmol) were dissolved in <NUM> of dry THF and transferred into a Parr reactor. The reactor was purged with N<NUM> followed by CO<NUM> and then pressurized with CO<NUM> up to <NUM> bar. The reaction was carried out under stirring at <NUM> for <NUM>. After the reaction, the reactor was cooled to room temperature and depressurized. THF was removed under reduced pressure and the crude product was then dissolved in ethyl acetate and filtered to afford the pure white product and a dark brown solution. Dark brown filtrate was passed through a pad of silica gel using ethyl acetate: petroleum ether (<NUM>:<NUM>) as eluent and solvent removed under reduced pressure to afford the remaining product (<NUM>, <NUM>%).

Preparation of pyridine-<NUM>,<NUM>-dicarboxylic acid chloride in DMF solution: To a round bottom flask connected with condenser, pyridine-<NUM>,<NUM>-dicarboxylic acid (<NUM>, <NUM> mmol), thionyl chloride (SOCl<NUM>) (<NUM>, <NUM> mmol) and <NUM> of DMF (catalytic amount) were added and the reaction was heated at <NUM> under argon for <NUM>. After that a colorless solution was obtained. The solvent together with excess thionyl chloride were removed under vacuum. The remained pyridine-<NUM>,<NUM>-dicarboxylic acid chloride was redissolved in <NUM> of anhydrous DMF.

To a solution of the reaction mixture of Et<NUM>N (<NUM>, <NUM> mmol) and glycerol carbonate (<NUM>, <NUM> mmol) in <NUM> of THF were added slowly the pyridine-<NUM>,<NUM>-dicarboxylic acid chloride in DMF solution at <NUM>. After stirring at room temperature for <NUM>, the reaction was heated at <NUM> for <NUM>. The reaction was quenched by addition of water (<NUM>). The product bis((<NUM>-oxo-<NUM>,<NUM>-dioxolan-<NUM>-yl)methyl)-pyridine-<NUM>,<NUM>-dicarboxylate was precipitated out from reaction mixture. The solids were collected, filtered and washed with water (<NUM>*<NUM>) and with THF (<NUM>*<NUM>) to give <NUM> (<NUM> mmol) of off-white solids (<NUM> % yield) which were characterized by <NUM>H-NMR, <NUM>C-NMR and HRMS. <NUM>H NMR (<NUM>, DMSO-d<NUM>) δ <NUM> - <NUM> (m, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> (dd, J = <NUM>, <NUM>, <NUM>); <NUM>C NMR (<NUM>, DMSO-d<NUM>) δ <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> HR-MS (ESI+): Calcd. for C<NUM>H<NUM>NO<NUM> [M+Na]+: <NUM>; Found: <NUM>.

Linear hydroxypolyurethane structures were synthesized by polyaddition of the prepared cyclic biscarbonates with various readily available diamines, as shown in Scheme <NUM>. <CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

In the synthesis of PHUs of the present application, the cyclic biscarbonate (e.g. <NUM>) and two drops of mesitylene (as internal standard) were taken into a (e.g. <NUM>) glass reactor and the content was dissolved in anhydrous DMF (e.g. <NUM> or <NUM>) while stirring on an oil bath at <NUM> (oil bath temperature). The solution was then purged with nitrogen for <NUM>-<NUM>. A solution of the diamine (<NUM> mol equiv) was prepared separately in anhydrous DMF, purged with nitrogen and charged into the reaction tube to initiate the reaction.

For polymerizations using less soluble diamines (e.g. XDA), the diamine was first dissolved in dry DMF at <NUM> and then equimolar quantity of cyclic biscarbonate monomer solution (nitrogen purged) was added to it. Reaction mixture was then allowed to stir for <NUM>. Time to time samples were collected by syringe to monitor monomer conversion by <NUM>H NMR spectroscopy. Finally, the reaction mixture was cooled down to room temperature and the polymer was precipitated using excess diethyl ether. Light brown polymer was then dried under air followed by heating at <NUM> in high vacuum oven. A small amount of polymer was re-dissolved in small amount of dry DMF, re-precipitated using ether and dried before the final characterization by gel permeation chromatography (GPC) using DMF as eluent and NMR spectroscopy.

<NUM>H NMR spectra were recorded on a <NUM> Bruker Ultra-Shield AVANCA 400SB spectrometer. Mesitylene or residual solvent peaks were used as internal standard.

Number average molecular weight (Mn), peak molecular weight (Mp) and polydispersity index (PDI) analysis of polymers synthesized according to the method disclosed herein were performed in size exclusion chromatography (SEC) systems using DMF as solvent. The DMF GPC system was equipped with Waters <NUM> HPLC pump, Waters <NUM> plus autosampler, Waters <NUM> refractive index (RI) detector, two PLgel <NUM> mixed-C columns. The eluent flow rate was <NUM>/min and the columns were maintained at <NUM>. The injected sample solution concentration was <NUM>/ ml and injected volume was <NUM>µl.

The details of the polymerization conditions and GPC data of the PHUs synthesized according to the method disclosed herein are provided in Table <NUM> as follows.

<NUM>H NMR spectra (in DMSO-d<NUM>) of polyhydroxyurethanes (PHUs) obtained using different bis-carbonate and bis-amine monomers according to the method disclosed herein are provided in <FIG>. <FIG> is <NUM>H NMR spectrum (in DMSO-d<NUM>) of polyhydroxyurethanes (PHUs) obtained using FBC-<NUM> and FBA. <FIG> is <NUM>H NMR spectrum (in DMSO-d<NUM>) of polyhydroxyurethanes (PHUs) obtained using FBC-<NUM> and FBA. <FIG> is<NUM>H NMR spectrum (in DMSO-d<NUM>) of polyhydroxyurethanes (PHUs) obtained using HFBC and DAP. <FIG> is <NUM>H NMR spectrum (in DMSO-d<NUM>) of polyhydroxyurethanes (PHUs) obtained using PBC and XDA.

GPC chromatogram of polyhydroxyurethanes (PHUs) obtained by the polymerization of FBC-<NUM> and FBA is provided in <FIG>.

FBC-<NUM> and two drops of mesitylene (as internal standard) were taken into a glass tube and the content was dissolved in anhydrous DMF while stirring on an oil bath at <NUM> (oil bath temperature). The solution was then purged with nitrogen for <NUM>-<NUM>. A solution of the diamine (<NUM> equiv) was prepared separately in anhydrous DMF, purged with nitrogen and charged into the reaction tube to initiate the reaction. Reaction mixture was then allowed to stir for <NUM>. Time to time samples were collected by syringe to monitor monomer conversion by <NUM>H NMR spectroscopy. Finally, the reaction mixture was cooled down to room temperature and the polymer was precipitated using excess diethyl ether. Light brown polymer obtained was then dried under air followed by heating at between <NUM> to <NUM> in high vacuum oven. A small amount of polymer was re-dissolved in small amount of dry DMF, re-precipitated using ether and dried before the final characterization by GPC (DMF eluent) and NMR spectroscopy.

The details of the polymerization conditions and GPC data for FBC-<NUM> based PHUs are provided in Table <NUM> as follows.

FBC-<NUM> and two drops of mesitylene (as internal standard) were taken into a glass tube and the content was dissolved in anhydrous DMF while stirring on an oil bath at <NUM> (oil bath temperature). The solution was then purged with nitrogen for <NUM>-<NUM>. A solution of the diamine (<NUM> mol equiv) was prepared separately in anhydrous DMF, purged with nitrogen and charged into the reaction tube to initiate the reaction. Reaction mixture was then allowed to stir for <NUM>. Time to time samples were collected by syringe to monitor monomer conversion by <NUM>H NMR spectroscopy. Finally, the reaction mixture was cooled down to room temperature and the polymer was precipitated using excess diethyl ether. Light brown polymer obtained was then dried under air followed by heating at <NUM> in high vacuum oven. A small amount of polymer was re-dissolved in small amount of dry DMF, re-precipitated using ether and dried before the final characterization by GPC (DMF eluent), DSC (Tg = <NUM>-<NUM>) and NMR spectroscopy. The details of the polymerization conditions and GPC data for the gram scale synthesis of FBC-<NUM> based PHU are provided in Table <NUM> as follows. The GPC chromatogram of PHU obtained by the polymerization of FBC2 and DAP is provided in <FIG>.

FBC-<NUM> (<NUM>, <NUM> mmol) was dissolved in <NUM> of dry DMF in a <NUM> two neck flask. The flask was purged with argon gas and heated to <NUM>. Mesitylene was added as an internal reference and a small sample of mixture was taken to be analysed by <NUM>H NMR and labelled as <NUM>. Pentane-<NUM>,<NUM>-diamine [DAP] (<NUM>, <NUM> mmol) was dissolved in <NUM> of DMF and added into round bottom flask. The reaction was stirred for <NUM>-<NUM> with sample being taken at <NUM>, <NUM>, <NUM>, <NUM>, <NUM> for NMR analysis. Reaction mixture was added drop by drop into glass bottle containing diethyl ether (<NUM>) with stirring. Product was washed further with diethyl ether (<NUM> x <NUM>) before drying overnight in a vacuum oven at <NUM> (<NUM>, <NUM>%). GPC: Mn <NUM>/mol, Mp <NUM>/mol, PDI <NUM>.

PBC-<NUM> and two drops of mesitylene (as internal standard) were taken into a glass tube and the content was dissolved in anhydrous DMF while stirring on an oil bath at <NUM> (oil bath temperature). The solution was then purged with nitrogen for <NUM>-<NUM>. A solution of the diamine (<NUM> equiv) was prepared separately in anhydrous DMF, purged with nitrogen and charged into the reaction tube to initiate the reaction. Reaction mixture was then allowed to stir for <NUM>. Time to time samples were collected by syringe to monitor monomer conversion by <NUM>H NMR spectroscopy. Finally, the reaction mixture was cooled down to room temperature and the polymer was precipitated using excess diethyl ether. Light brown polymer was then dried under air followed by heating at <NUM> in high vacuum oven. A small amount of polymer was re-dissolved in small amount of dry DMF, re-precipitated using ether and dried before the final characterization by GPC (DMF eluent) and NMR spectroscopy.

The details of the polymerization conditions and GPC data for PBC-<NUM> based PHU are provided in Table <NUM> as follows.

The novel PHUs obtained can be further functionalized through the hydroxyl group to achieve new functionalized PHUs having desired properties such as hydrophilicity, hydrophobicity, oil solubility and dispersibility in water and oil for various applications. The functionalization could lead to neutral, anionic, cationic or zwitterionic polymers. This strategy could also be applied to any polyhydroxyurethanes obtained through the reaction between any bis/multi-carbonate and any bis/multi-amine and the corresponding obtained PHU having one or more unfunctionalised primary or secondary hydroxyl groups. The functionalization strategy includes, but is not limited to esterification, sulphonylation, phosphorylation, zwitterion formation and grafting suitable molecular entities/oligomers/polymers. The following examples illustrate the said component of the invention.

The hydroxyl groups of the PHUs were functionalized introducing anionic phosphate ester or alkylsulfonate groups as pendants. The counter cations can be varied and the degree of functionalization optimized to modify solubility, dispersion and crosslinking characteristics of the PHUs in water at different pHs as well as in various organic solvents.

To a solution of a representative PHU (<NUM>) in anhydrous DMF (<NUM>) and acetonitrile (<NUM>) mixture was added with the desired amount of trichloroacetonitrile (TCAN, <NUM> equiv. Desired amount of tetra-n-butylammonium dihydrogen phosphate (TBAP) was dissolved separately in anhydrous acetonitrile (<NUM>) and added into the polymer solution dropwise. The reaction mixture was stirred at room temperature for <NUM>. Solvent was removed under reduced pressure and the residue was re-dissolved in a small amount of acetonitrile (<NUM>). The phosphate-functionalized PHU was precipitated out using diethyl ether (<NUM>) as anti-solvent. Characterization was done using <NUM>H and <NUM>P NMR (DMSO-d<NUM>), TGA, DSC and DLS (Table <NUM>). <NUM>H NMR showed n-butyl peaks at <NUM>, <NUM> and <NUM> ppm. Multiple peaks between <NUM> - <NUM> ppm were observed in <NUM>P NMR. Preliminary solubility data are demonstrated in Table <NUM>.

To a solution of a representative PHU (<NUM>) (Table <NUM>) in anhydrous DMF (<NUM>) was added with <NUM>,<NUM>-butane sultone (<NUM> equiv). <NUM>% sodium hydride in oil (<NUM> equiv) was then slowly added to the reaction mixture at room temperature and was stirred at room temperature for about <NUM> before heating up to <NUM> and stirred for another <NUM>. The reaction mixture was cooled to <NUM> and <NUM> methanol was added to quench the reaction. After the solvent was removed under reduced pressure and the solid was washed with diethyl ether (<NUM> x <NUM>) characterization/preliminary solubility studies were done using <NUM>H NMR in DMSO-d<NUM> with butyl peaks observed at <NUM> and <NUM> ppm (Tables <NUM> and <NUM>).

To a representative PHU based on FBC-<NUM> and DAP (<NUM>, <NUM> mmol) in anhydrous DMF (<NUM>) solution, triethylamine (<NUM>, <NUM> mmol) was added followed by ethylene chlorophosphate (<NUM>, <NUM> mmol) at room temperature. After stirring the reaction at RT for <NUM>, the solvent was removed and the product precipitated using water. The precipitate obtained was washed with water (<NUM> x <NUM>) and with diethyl ether. Based on the <NUM>H NMR, the hydroxyl groups in the PHU were completely reacted. In <NUM>P NMR a single phosphorous peak was observed at <NUM> ppm. Phosphocholine functionalized PHUs can be obtained by the reaction of this product with trimethylamine.

PHUs can be functionalized with amino acids or peptides or proteins by any standard esterification protocols introducing amino and thiol pendant groups. The degree of functionalization can be tuned. The thiol groups can facilitate reversible self-crosslinking or cross linking with other substrates such as peptides by disulfide chemistry.

A representative PHU based on FBC-<NUM> and DAP (<NUM>, <NUM> mmol) in anhydrous DMF (<NUM>) solution was added to the desired amino acid chloride hydrochloride (<NUM> mmol) in DMF followed by (<NUM>, <NUM> mmol) triethylamine at room temperature. After <NUM> of stirring, the reaction was stopped and subjected to different methods of work-up.

Method A: <NUM> of water was added to quench the reaction. After removing the solvent, the residue obtained was dissolved in water (<NUM>). The aqueous layer was washed with ethyl acetate (<NUM> x <NUM>) and evaporated to dryness under reduced pressure and then re-dissolved in small amount of acetone (<NUM>). The functionalized PHU was precipitated out using diethyl ether (<NUM>) as anti-solvent.

Method B: <NUM> of water was added at ambient temperature to quench the reaction. After removing the solvent, the residue obtained was dissolved in DCM (<NUM>) and was washed with dilute bicarbonate solution (<NUM>) followed by water (<NUM>). The organic layer was separated and dried with sodium sulfate, filtered and evaporated to dryness under reduced pressure. The residue was re-dissolved in DCM (<NUM>). The functionalized PHU was precipitated out using diethyl ether (<NUM>) as anti-solvent.

Method C: <NUM> of water was added at ambient temperature to quench the reaction. The polymer precipitated out from the reaction was collected by filtration. The polymer was redissolved in DMF (<NUM>) and chloroform was used as anti-solvent to re-precipitate the polymer which was then dried under vacuum (<NUM> (yield <NUM> %)) as a brown syrup. Characterization was done using <NUM>H NMR.

The introduction of pendant medium and long chain alkyl or alkenyl or arylalkyl or arylalkenyl functionalities to PHUs by esterification using fatty acid/ or carboxylic acid derivatives by standard esterification protocols resulting in hydrophobic isocyanate free polyurethanes which are oil soluble/dispersible and air/photo/thermo crosslinkable and photoreversibly crosslinkable is reported herein.

A representative PHU based on FBC-<NUM> and DAP (<NUM>, <NUM> mmol) in anhydrous DMF (<NUM>) solution was added to the desired acylation reagent (<NUM> mmol) followed by (<NUM>, <NUM> mmol) triethylamine at room temperature. After <NUM> of stirring, <NUM> of water was added to quench the reaction. After removing the solvent, the residue obtained was dissolved in DCM (<NUM>). The organic layer was washed with dilute bicarbonate solution (<NUM>) followed by water (<NUM>). The organic layer was separated and dried over sodium sulfate, filtered and evaporated to obtain the expected product.

To a representative PHU based on FBC-<NUM> and DAP (<NUM>, <NUM> mmol) in anhydrous DMF (<NUM>) solution, lactide (<NUM>, <NUM> mmol) and DMAP (<NUM>, <NUM> mmol) were added at room temperature. After <NUM> of stirring at <NUM>, the solvent was removed and the residue was subsequently dissolved in DCM (<NUM>) and precipitated out using diethyl ether as the anti-solvent (<NUM>). The product is subsequently washed two times with diethyl ether and dried to obtain the product (<NUM>, <NUM>%). Characterization was done using <NUM>H NMR in MeOH-d4 (Lactyl peaks observed at <NUM>, <NUM> and <NUM> ppm) and GPC (Mn = <NUM>/mol, Mp = <NUM>/mol, PDI = <NUM>.

Different types of polymers can be grafted from or to PHUs resulting in novel functional materials. In one of these approaches exemplified herein, polymers were grafted from PHUs by ring opening polymerization using lactide and lactone to form PHU-graft co-polymers. Other types of ROP using lactams, cyclic carbonates are also possible. An example for the "graft to" approach can be demonstrated using grafting PDMS to PHUs resulting in new functional PHUs, which can be used in anti-smudge coatings. An example on using furan based PHUs for grafting via Diel's- Alder reaction (DA reaction) is also demonstrated. Similarly, peptides or proteins can also be grafted to PHUs resulting in stimuli responsive active delivery, functional coatings materials for biomedical devices etc. For example, DA reaction of maleimide functionalized peptides or proteins to furan based PHUs or coupling of cysteine modified PHU with peptides containing cysteine residue by disulfide chemistry.

To a representative PHU based on FBC-<NUM> and DAP (<NUM>, <NUM> mmol) in anhydrous DMF (<NUM>) solution, lactide (<NUM>, <NUM> mmol) and DMAP (<NUM>, <NUM> mmol) were added at room temperature. After <NUM> of stirring at <NUM>, the solvent was removed and the residue was subsequently dissolved in DCM (<NUM>) and precipitated out using diethyl ether as the anti-solvent (<NUM>). The product is washed two times with diethyl ether and dried to obtain the product (<NUM>, <NUM>%). Characterization was done using <NUM>H NMR in CDCl<NUM> with lactyl peaks observed at <NUM>, <NUM>, <NUM> & <NUM> ppm and GPC: Mn = <NUM>/mol, Mp = <NUM>/mol, PDI = <NUM>.

To a solution of a representative PHU based on FBC-<NUM> and DAP (<NUM>) in anhydrous DMF (<NUM>) ε-caprolactone (<NUM>, <NUM> equiv) and trifluromethanesulfonimide (<NUM>, <NUM> equiv) were added and the reaction mixture was stirred at <NUM> for <NUM>. Solvent was removed under reduced pressure and the product re-dissolved in small amount of chloroform (<NUM>). Product was precipitated out using diethyl ether (<NUM>) as anti-solvent. Characterization was done using <NUM>H NMR in CDCl<NUM> with caproyl peaks observed at <NUM>, <NUM>, and <NUM>.

To a <NUM> reaction flask filled with Argon was added oxalyl chloride (COCl)<NUM> (<NUM>, <NUM> mmol). Subsequently, hydroxyl-terminated polydimethylsiloxane (Mn ~ <NUM>) PDMS-OH (<NUM>, <NUM> mmol) was added dropwise into the oxalyl chloride. The reaction mixture was allowed to stir at room temperature for <NUM>. Unreacted oxalylchloride and volatile impurities were removed by keeping the reaction mixture under vaccum at room temperature for <NUM> and at <NUM> for <NUM> to yield PDMS-OCOCOCI as a clear liquid.

In the next step, a represeantive PHU polymer based on FBC-<NUM> and DAP (<NUM>) was dissolved in anhydrous DMF (<NUM>) followed by addition of <NUM> THF solution of PDMS-OCOCOCI. The reaction mixture was stirred at room temperature for <NUM> and quenched with <NUM> of water. The solvent was removed under vaccum and the residue redissolved in <NUM> of chloroform and was washed with bicarbonate solution (<NUM>) followed by water (<NUM>). After concentrating this solution to <NUM>, the petroleum ether was added to precipitate out <NUM> (<NUM>% yield) of the product as a yellow syrup. Characterization was done using <NUM>H NMR in CDCl<NUM> with siloxane peak observed as large board singlets at <NUM> ppm and the furan peak was observed as a singlet at <NUM> ppm.

To a solution of a representative PHU based on FBC-<NUM> and DAP (<NUM>, <NUM> mmol based on mole of furan) in DMF (<NUM>) was added PLA-M (<NUM>, Mn-<NUM>, <NUM> mmol based on mole of maleimide). The reaction mixture was stirred at <NUM> for <NUM> hours. After cooling to room temperature, the reaction mixture was added into diethyl ether to precipitate the polymer. The crude polymer was washed with ethyl acetate to remove the unreacted PLA-M. The purified polymer was obtained as white solid (<NUM>, yield <NUM>%). <NUM>H NMR (<NUM>, DMSO) δ <NUM> (br, <NUM>), <NUM> (br, <NUM>), <NUM> (br, DA adduct peak), <NUM> (br, <NUM>), <NUM> (br, <NUM>), <NUM> - <NUM> (br, <NUM>), <NUM> (br, PLA peak), <NUM> - <NUM> (m, <NUM>), <NUM> - <NUM> (m, <NUM>), <NUM> (br, <NUM>), <NUM> (m, <NUM>), <NUM> - <NUM> (m, <NUM>).

Various embodiments of the present disclosure provide a green and sustainable strategy to produce cyclic biscarbonates and polyhydroxyurethanes by using precursor compounds derived from a bio-based source. In various embodiments, the precursor compound, monomer and/or reaction product may be partially bio-based/bio-derived or fully bio-based/bio-derived. In various embodiments of the methods disclosed herein, the process does not involve the use of toxic isocyanates and phosgene, thereby making the production process friendly to the environment.

In various embodiments thereof, the compound (i.e. monomer) and reaction product (i.e. polymer) disclosed herein are high value products for specialty applications such as coating, foams and adhesives, which will not only further value-add bio-feedstocks supporting biorefineries but also provide alternative sustainable materials for future applications.

Various embodiments of the present disclosure provide non-isocyanate polyhydroxylurethanes (NIPUs/PHUs) having high thermal and hydrolytic stability, enhanced adhesion properties and are chemically resistant to non-polar solvents. Various embodiments of the present disclosure provide compounds that are capable of serving as monomers in a polymerization reaction and that comprise aromatic units that are atypical of cyclic biscarbonates known in the art. In various embodiments therefore, the reaction products of these monomers and polymers disclosed herein may be in the form of a new emerging class of functional isocyanate free polyurethanes and that can be used in a wide array of applications such as in the manufacturing of foams, solvent/water borne coating, adhesives in the building and construction, automotive, packaging, textiles, fibers, apparel, and electronics industry etc; in applications such as pigment/hydrophobic material dispersing agents, film formers, gelling agents, rheology modifiers, oil thickners etc; in personal care industry and in applications such as antifouling coating and drug delivery in biomedical industries. The present disclosure has demonstrated the principles involved, and opens the way for further scale-up in many applications.

Claim 1:
A compound represented by general formula (Ib):
<CHM>
wherein
ring A is selected from the group consisting of thiophene, pyrrole, oxazole, isoxazole, isothiazole, tetrahydrofuran, tetrahydrothiophene, pyrrolidine, pyridine, pyrone, pyridazine, pyrimidine, pyrazine, triazine, piperidine and piperazine;
Y<NUM> and Y<NUM> are each independently selected from the group consisting of:
a single bond,

        -Z-O-Z-,

        -Z-NRb-Z-,

        -Z-O-C(=O)-Z-, -Z-C(=O)-O-Z-,

        -Z-NRb-C(=O)-Z-, -Z-C(=O)-NRb-Z-,

        -Z-NRb-C(=O)-O-Z-, -Z-O-C(=O)-NRb-Z-;

where each Z is independently selected from the group consisting of a single bond, optionally substituted saturated aliphatic chain and optionally substituted unsaturated aliphatic chain; and
where Rb is H or C<NUM>-C<NUM> alkyl.