Cyclic-moiety containing compounds and polymers comprising the same

Abstract

The present invention provides compounds comprising a cycling moiety, such as furan. Polymers made from such monomers are also provided.

Description

Cyclic-moiety containing compounds and polymers comprising the sameBACKGROUND OF THE INVENTION

[0001] The present disclosure relates to compounds comprising cyclic organic moieties.

[0002] The present invention concerns compounds comprising cyclic organic moieties. More particularly, but not exclusively, this invention concerns a compound. The invention also concerns a method of making a compound, a polymer and a method of making a polymer.

[0003] There is a desire to be able to produce polymers from monomers comprising cyclic organic monomers quickly, efficiently and / or inexpensively, optionally using materials that are readily-available, and / or available from renewable sources. This is not always possible, however. It has been recently discovered, however, that diformylfuran may be readily produced from renewable sources, in this case, monosaccharides, disaccharides and polysaccharides.

[0004] The present invention seeks to mitigate the above-mentioned problems. Alternatively or additionally, the present invention seeks to provide an improved compound, polymer and / or a method of making a polymer.SUMMARY OF THE INVENTION

[0005] The present invention provides compound A, comprising (i) or (ii):where X=O, S or NR10, Y=N or CR10where R10is H or optionally substituted alkyl, each substituent optionally being selected from the group consisting of -OH, -F, -Cl, -Br, -I, and -CN, R10optionally being straight chain or branched,at least two of R1, R2, R3and R4or at least two of R5, R6, R7, R8and R9are of structure (in):(Hl)Where, if (i) is present, the at least two of R1, R2, R3and R4may be the same or different;Where, if (ii) is present, the at least two of R5, R6, R7, R8and R9may be the same or different;Where A, G and M are carbon, and A is attached to the ring structure of (i) or (ii);There is a single or double carbon-carbon bond between A and G;And if there is a single bond between A and G, there may optionally also be an epoxy(-O-) group between A and G;R11is selected from the group consisting of H and optionally substituted alkyl each substituent optionally being selected from the group consisting of -OH, -F, -Cl, -Br, -I, and -CN;If there is a double carbon-carbon bond between A and G, or if there is a single carbon- carbon-bond between A and G, and there is an epoxy group between A and G, then R12and R14are absent;If there is a single carbon-carbon bond between A and G, and no epoxy group between A and G, then R12and R14are present and are independently selected from the group consisting of -OH, H and optionally substituted alkyl, each substituent optionally being selected from the group consisting of -OH, -F, -Cl, -Br, -I, and -CN;W is selected from the group consisting of -OH, NHR17, NR19and O, wherein if W is NR19or O, then there is a double bond between O or NR19and M; where R17and R19may be individually selected from H and optionally substituted alkyl, each substituent optionally being selected from the group consisting of -OH, -F, -Cl, -Br, -I, and -CN,Wherein if W is O or NR19and if there is a double bond between the O or NR19and M, then R16is absent;Wherein R15(and R16, if present) are independently selected from the group consisting of H and optionally substituted alkyl, each substituent optionally being selected from the group consisting of -OH, -F, -Cl, -Br, -I, and -CN, whereas R15may also be -OH if W is O;Wherein R13is a group comprising up to 30 carbon atoms, and comprises one or more alkyl, alkenyl, cycloalkyl, aryl, alkynyl, alkanediyl, alkenediyl, cycloalkanediyl, arenediyl, alkynediyl, each of which may optionally be substituted, optionally with one or more linking groups therebetween, optionally selected from the group consisting of -S-, -O-, - O-C(O), -C(O)-O-, each substituent optionally being selected from the group consisting of -OH, -F, -Cl, -Br, -I and -CN,If (i) is present, then those of R1, R2, R3and R4not being (iii) are identical or different and are individually selected from the group consisting of H, halide and an optionally substituted alkyl group, each substituent optionally being selected from the group consisting of -OH, -F, -Cl, -Br, -I, and -CN,If (ii) is present, then those of R5, R6, R7, R8and R9not being (iii) are identical or different and are individually selected from the group consisting of H, halide, -SO3R18and an optionally substituted alkyl group, where R18is H or an optionally substituted alkyl group, each substituent optionally being selected from the group consisting of -OH, -F, -Cl, -Br, -I, and -CN.

[0006] The applicant has discovered that it is possible to synthesise compounds comprising cyclic moieties (i) or (ii) using readily available materials, such as diformylfuran, which may be synthesised from environmentally-secure sources, such as polysaccharides. For the avoidance of doubt, R14(if present) is bonded to G and R16(if present) is bonded to M.

[0007] If (i) is present, then preferably two (and only two) of R1, R2, R3and R4have the structure (iii). Preferably, R1and R2have the structure (iii). Preferably, the two groups having the structure (iii) have the same structure. This facilitates simple synthesis of compound A. If (i) is present, it is preferred that X is O.

[0008] If (ii) is present, then preferably two (and only two) of R5, R6, R7, R8and R9have the structure (iii). Optionally, R5and R9have the structure (iii), or optionally R5and R6have the structure (iii). Preferably, the two groups having the structure (iii) have the same structure. This facilitates simple synthesis of compound A.

[0009] If structure (i) is present, then X is preferably O, preferaby with R1and R2having the structure (iii); such a structure may be obtained from diformylfuran, which may be readily obtained from renewable sources, such as polysaccharides

[0010] R10may optionally be H or unsubstiuted alkyl; optionally H or unsubstituted Ci- C12 alkyl; optionally H or unsubstituted Ci-Ce alkyl, and optionally H.

[0011] If (i) is present, those of R1, R2, R3and R4not being (iii) are identical or different, and are optionally selected from the group consisting of H, halide or an unsubstituted alkyl group. Those of R1, R2, R3and R4not being (iii) may be identical or different, and are optionally selected from the group consisting of H or an unsubstituted alkyl group. Those of R1, R2, R3and R4not being (iii) may be identical or different, and are optionally selected from the group consisting of H or an unsubstituted C1-C12 alkyl group. Those of R1, R2, R3and R4not being (iii) may be identical or different, and are optionally selected from the group consisting of H or an unsubstituted Ci-Ce alkyl group. Those of R1, R2, R3and R4not being (iii) may be H.

[0012] If (ii) is present, then those of R5, R6, R7, R8and R9not being (iii) are identical or different and may optionally be selected from the group consisting of H, halide, -SO3R17or an unsubstituted alkyl group, where R17is H and an unsubstituted alkyl group. Those of R5, R6, R7, R8and R9not being (iii) are identical or different, and may optionally be selectedfrom the group consisting of H, -SO3R17and an unsubstituted alkyl group, where R17is H or an unsubstituted alkyl group. Those of R5, R6, R7, R8and R9not being (iii) are identical or different and may optionally be selected from the group consisting of H, halide, and an unsubstituted alkyl group. Those of R5, R6, R7, R8and R9not being (iii) are identical or different and may optionally be selected from the group consisting of H and an unsubstituted alkyl group. Those of R5, R6, R7, R8and R9not being (iii) are identical or different and may optionally be selected from the group consisting of H and an unsubstituted C1-C12 alkyl group. Those of R5, R6, R7, R8and R9not being (iii) are identical or different and may optionally be selected from the group consisting of H and an unsubstituted Ci-Ce alkyl group. Those of R5, R6, R7, R8and R9not being (iii) may optionally be H.

[0013] Optionally, R11, R12(if present) and R14(if present) are independently selected from the group consisting of -OH, H or unsubstiuted alkyl; optionally -OH, H or unsubstituted C1-C12 alkyl; optionally -OH, H or unsubstituted Ci-Ce alkyl. Optionally, R11, R12(if present) and R14(if present) are -OH or H, and optionally H.

[0014] Optionally, R12and R14are absent and there is a double carbon-carbon bond between A and G, or a single carbon-carbon bond between A and G and also an epoxy group between A and G.

[0015] Optionally, R15and R16(if present) are independently selected from the group consisting of H or unsubstiuted alkyl, optionally H or unsubstituted C1-C12 alkyl, optionally H or unsubstituted Ci-Ce alkyl. Optionally, R15and R16(if present) are H.

[0016] W is optionally selected from the group consisting of -OH, NHR17, NR19and O, wherein if W is NR19or O, then there is a double bond between O or NR19and M; where R17and R19may be individually selected from H and unsubstituted alkyl. W is optionally selected from the group consisting of -OH, NHR17, NR19and O, wherein if W is N or O, then there is a double bond between O or N and M; where R17and R19may be unsubstituted alkyl. W is optionally selected from the group consisting of -OH, NHR17, O, wherein if W is O, then there is a double bond between O and M; where R17may be unsubstituted alkyl. W is optionally selected from the group consisting of -OH and O, wherein if W is O, thenthere is a double bond between O and M. W is optionally -OH. W is optionally O, and there is a double bond between O and M.

[0017] R13optionally comprises one or more moieties suitable for taking part in a polymerisation reaction, optionally selected from the group consisting of C-C double bond, C-C triple bond, conjugated CC double bond, aldehyde, amine (primary or secondary), amide, alcohol, acid, acid chloride, epoxy, acetal, ketal, hemiacetal, hemiketal, ether, ester and cyano.

[0018] If R13optionally comprises one or more moieties suitable for taking part in a polymerisation reaction, then it is preferred that at least two of R1, R2, R3and R4or at least two of R5, R6, R7, R8and R9are:(in)And at least two R13groups comprise one or more moieties suitable for taking part in a polymerisation reaction, such as an unsaturated carbon-carbon bond. The applicant has discovered that such an arrangement is a convenient arrangement for the manufacture of polymers.

[0019] R13optionally comprises one or more alkyl, alkenyl, alkanediyl, alkenediyl, cycloalkanediyl and cycloalkyl optionally with one or more linking groups therebetween, optionally -O-.

[0020] R13optionally comprises optionally-substituted alkyl cycloalkyl, alkyl or alkenyl, which may be linear or branched. Each substituent may optionally be selected from the group consisting of -OH, -F, -Cl, -Br, -I, -CN, aldehyde and ketone.

[0021] The alkyl cycloalkyl, alkyl or alkenyl group may comprise up to 30 carbon atoms, optionally up to 25 carbon atoms, optionally up to 20 carbon atoms and optionally up to 15 carbon atoms. The alkyl cycloalkyl, alkyl or alkenyl group may comprise at least 5 carbonatoms, optionally at least 8 carbon atoms, optionally at least 10 carbon atoms and optionally at least 12 carbon atoms. The alkyl cycloalkyl group may comprise an optionally- substituted cyclohexyl moiety. The alkyl cycloalkyl group may comprise an optionally- substituted -(CH2)n- moiety, where n is from 1 to 10, optionally from 1 to 8, optionally from 3 to 8 and optionally from 3 to 6.

[0022] R13may optionally comprise a C3-20 alkenyl group, optionally a C6-20 alkenyl group, optionally a Ce-15 alkenyl group and optionally a C6-12 alkenyl group. The alkenyl group is optionally substituted, but is preferably unsubstituted. The alkenyl group may be straight or branched.

[0023] The C=C double bond may be located at any position in the alkenyl group. The C=C double bond may be a terminal group, for example.

[0024] The group of structure (iii) may be selected from the group consisting of structures (iv), (v), (vi), (vii), (viii), (ix), (x), (xi), (xii), (xiii), (xiv) or (xv):(xiv)

[0025] Groups R11, R12, R13, R14, R15, R16, R17and R19may be as described above.

[0026] In particular, R11and R15are individually selected from H and unsubstituted C1-12 alkyl, optionally H and unsubstituted C1-6 alkyl, and are optionally both H.

[0027] In particular, R12and R14are individually selected from -OH, H and unsubstituted C1-12 alkyl, optionally OH, H and unsubstituted C1-6 alkyl, optionally OH and H, and are optionally both H.

[0028] R16is individually selected from H and unsubstituted C1-12 alkyl, optionally H and unsubstituted C1-6 alkyl, and optionally H.

[0029] In particular, R11, R15and R16(if present) are individually selected from H and unsubstituted C1-12 alkyl, optionally H and unsubstituted C1-6 alkyl. Optionally, R11, R15, R16and R14(if present) are H; and R12(if present) and R14(if present) are individually selected from -OH, H and unsubstituted C1-12 alkyl, optionally -OH, H and unsubstituted C1-6 alkyl, optionally selected from -OH and H, and are optionally H. Optionally, R11, R15, R16(if present), R12(if present) and R14(if present) are H

[0030] R13may optionally comprise a C3-20 alkenyl group, optionally a C6-20 alkenyl group, optionally a Ce-15 alkenyl group and optionally a Ce-12 alkenyl group. The alkenyl group is optionally substituted, but is preferably unsubstituted. The alkenyl group may be straight or branched.

[0031] Compound A comprising structure (iv) may be readily synthesised using an aldol condensation reaction between a core-providing molecule comprising at least one aldehyde group (such as diformylfuran) and an aldehyde, such as 10-undecenal.

[0032] According to a second aspect of the invention there is also provided a method of forming compound A, the method comprising providing, in admixture, a compound of formula (xvi) or (xvii) with an aldehyde or ketone.where X and Y are as defined in accordance with the first aspect of the present invention; where, if compound (xvi) is used, then two or more, and optionally only two, of R20, R21, R22and R23are -C(O)Rn, where said two or more, and optionally said only two of R20, R21, R22and R23are the same or different; where, if compound (xvii) is used, then two or more, and optionally only two, of R24, R25, R26, R27and R28are -C(O)Rn, where said two or more, and optionally said only two of R24, R25, R26, R27and R28are the same or different.

[0033] Providing, in admixture, a compound of formula (xvi) or (xvii) with an aldehyde or ketone forms a compound of formula A comprising at least two, and optionally only two, groups of structure (iv).

[0034] Examples of the second aspect of the present invention may provide a method that is simple and gives a good yield in relatively benign conditions. The applicant anticipates that the method is potentially scalable, and that the energy requirements for the reaction may be relatively low. The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (v) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). This may comprise contacting the compound of formula A comprising at least two, and optionally only two, groups of structure (iv), with a reducing agent, such as LiAIFU or NaBH4.

[0035] The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (x) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). This may comprise contacting the compound of formula A comprising at least two, and optionallyonly two, groups of structure (iv), with a reducing agent, such as H2 in the presence of a suitable catalyst.

[0036] The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (vii) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). This is a reductive amination reaction. This may comprise contacting the compound of formula A comprising at least two, and optionally only two, groups of structure (iv), with a primary or secondary amine, for example, in the presence of Na(AcO)3BH, AcO, THF at room temperature.

[0037] The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (viii) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). This formation on an imine from an aldehyde may comprise contacting the compound of formula A comprising at least two, and optionally only two, groups of structure (iv), with an amine, such as a primary amine, optionally in mildly acidic conditions.

[0038] The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (vi) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). This may comprise forming a compound of formula A comprising at least two, and optionally only two, groups of structure (x) or of structure (v) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv).

[0039] The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xi) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). This may comprise forming a compound of formula A comprising at least two, and optionally only two, groups of structure (vii) or of structure (x) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv).

[0040] The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xii) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). This epoxidation reaction may be achieved using mCPBA (meta-chloroperoxybenzoic acid), for example.

[0041] The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xiii) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). This may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xii) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xiii) from a compound of formula A comprising at least two, and optionally only two, groups of structure (xii).

[0042] The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xiii) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). This may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (v) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xiii) from a compound of formula A comprising at least two, and optionally only two, groups of structure (v).

[0043] The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xiv) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). This may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xii) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xiv) from a compound of formula A comprising at least two, and optionally only two, groups of structure (xii).

[0044] The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xiv) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). This maycomprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (vii) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xiv) from a compound of formula A comprising at least two, and optionally only two, groups of structure (vii).

[0045] The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xv) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). This may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xii) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xv) from a compound of formula A comprising at least two, and optionally only two, groups of structure (xii).

[0046] The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xv) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). This may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (viii) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv). The method may comprise forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xv) from a compound of formula A comprising at least two, and optionally only two, groups of structure (viii).

[0047] According to a third aspect of the present invention, there is also provided a polymer comprising a plurality of residues derived from Compound A as described above in relation to the first aspect of the present invention.

[0048] The polymer may be a homopolymer. The polymer may be a copolymer that comprises a plurality of residues derived from Compound A and a plurality of residues derived from a different monomer.

[0049] The uses of the polymer according to the present invention would, to some extent, depend on the structure of that polymer. For example, if the polymer comprises epoxy groups, it may be used as an adhesive. Polymers comprises side chains comprising one or more ether groups may be used as surfactants, for example.

[0050] The polymer may have a Tgof at least -30°C, optionally at least -20°C, optionally at least -15°C and optionally at least -10°C.

[0051] The polymer may have a Tgof no more than 30°C, optionally no more than 20°C, optionally no more than 15°C and optionally no more than 10°C.

[0052] Tgmay be determined using scanning differential calorimetry, optionally using a heating rate of 10°C / min.

[0053] Mnmay optionally be at least 2000 g / mol, optionally at least 3000 g / mol and optionally at least 4000g / mol.

[0054] Mnmay optionally be no more than 40000 g / mol, optionally no more than 35000 g / mol, optionally no more than 30000 g / mol and optionally on more than 25000 g / mol.

[0055] Mwmay optionally be at least 3000 g / mol, optionally at least 4000 g / mol and optionally at least 5000g / mol.

[0056] Mwmay optionally be no more than 80000 g / mol, optionally no more than 70000 g / mol, optionally no more than 60000 g / mol and optionally on more than 50000 g / mol.

[0057] Mnand Mwmay be determined using THF as eluent and relative to polystyrene standards.

[0058] The poly dispersity index (Mw / Mn) may optionally be at least 1.0, optionally at least 1.2 and optionally at least 1.4.

[0059] The poly dispersity index (Mw / Mn) may optionally be no more than 5.0, optionally no more than 4.0 and optionally no more than 3.0.

[0060] The polymer may comprise residues of Compound A, Compound A optionally comprising at least two polymerisable unsaturated carbon-carbon groups (such as alkenyl or alkynyl groups). The polymer may comprise residues of Compound A, the two polymerisable unsaturated carbon-carbon groups having taken part in a polymerisation reaction to form a polymer.

[0061] The polymer may comprise a plurality of residues of Compound A, wherein Compound A comprises at least one group (and optionally two groups) of structure (iv), (v), (vi), (vii), (viii), (ix), (x), (xi), (xii), (xiii), (xiv) or (xv). The polymer will therefore comprise residues of group (iv), (v), (vi), (vii), (viii), (ix), (x), (xi), (xii), (xiii), (xiv) or (xv).

[0062] For example, if Compound A comprises at least two of structure (v) or (vi), then the polymer may optionally comprise residues of that Compound A, the polymer optionally comprising a residue of a bridging group (such as a di-acid or di-acid chloride) coupled to the — O atom of structure (v) or (vi).

[0063] For example, if Compound A comprises at least two of structure (iv) or (x), then the polymer may optionally comprise residues of that Compound A, the polymer optionally comprising a residue of a bridging group (such as a diamine) coupled to a residue of structure (iv) or (x) via an imine group.

[0064] According to a fourth aspect of the present invention, there is also provided a method of making a polymer in accordance with the third aspect of the present invention, the method comprising polymerising Compound A in accordance with the first aspect of the present invention.

[0065] The method may comprise providing a comonomer in admixture with Compound A, and polymerising the comonomer and Compound A.

[0066] Compound A may comprise at least two polymerisable unsaturated C-C groups (such as alkenyl or alkynyl groups). The method may comprise providing conditions to facilitate polymerisation of Compound A via reaction of the unsaturated C-C groups. A polymerisable unsaturated C-C group may be provided in the R13group. Compound A may comprise two such R13groups, each comprising a polymerisable unsaturated C-C group.

[0067] Compound A may optionally comprise at least two, and optionally only two, of groups having a structure (v) or (vi). In this case, the method may comprise contacting Compound A with a bridging compound comprising at least two acid or acid chloride groups. The acid or acid chloride groups may react with the -OH groups of Compound A to form a polymer.

[0068] Compound A may optionally comprise at least two, and optionally only two, of groups having a structure (iv) or (x). In this case, the method may comprise contacting Compound A with a bridging compound comprising at least two amine groups. The acid or acid chloride groups may react with the -OH groups of Compound A to form a polyimine.

[0069] It will of course be appreciated that features described in relation to one aspect of the present invention may be incorporated into other aspects of the present invention. For example, the method of the invention may incorporate any of the features described with reference to the apparatus of the invention and vice versa.

[0070] Embodiments of the present invention will now be described by way of example only.DETAILED DESCRIPTION

[0071] Whilst the present invention has been described and illustrated with reference to particular embodiments, it will be appreciated by those of ordinary skill in the art that the invention lends itself to many different variations not specifically illustrated herein. By way of example only, certain possible variations will now be described.

[0072] In an oven dried round bottom flask, diformylfuran (DFF) (742 mg, 5.979 mmole) was dissolved in 20 mL methanol with the assistance of a magnetic stirrer. Subsequently, 3 mL NaOH (IM) was injected and the solution was stirred for 5 minutes before adding 2 equiv. of 10-undecenal (undecylenic aldehyde, UA) (2012 mg, 11.958 mmole). The reaction was allowed to continue at room temperature and the progress of the reaction was monitored via TLC using n-hexane: ethyl acetate (80:20) as eluent. TLC showed complete conversion of DFF in an hour. IM HC1 was then added to adjust the pH to 7-8, followed by extraction of the aqueous (methanol) phase with n-hexane (30 mL x 3). The organic layers were combined and dried over anhydrous MgSO-i and filtered. After removal of the solvent in the rotovap, the crude aldol monomer was obtained as a yellow oil. The crude product was purified via column chromatography (silica gel, n-hexane: ethyl acetate 100:0 to 70:30) to give a bright pale-yellow oil, Compound 3, with a yield of 72%. TLC using n- hexane: ethyl acetate (80:20) gave an Rf of 0.30.

[0073] The formation of Compound 3 from 10-undecenal and diformylfuran is shown below.

[0074] The structure of Compound 3 was verified usingand13C NMR.

[0075] 'H NMR (500 MHz, CDC13, 5 in ppm): 9.49 (2H, H-l), 6.94 (2H, H-3), 6.88 (2H, H-2), 5.76 (2H, H-l l), 4.91 (4H, H-12), 2.65 (4H, H-4), 2.01 (4H, H-10), 1.45 (4H, H-5), 1.22-1.38 (16H, H-6 to H-9) (only one half of Compound 3 is shown)

[0076] 13C H} NMR (125 MHz, CDCh, 5 in ppm): 193.6 (C-a), 153.3 (C-c), 141.9 (C- e), 139.0 (C-m), 133.6 (C-d), 118.6 (C- b), 114.2 (C-n), 33.7 (C-l), 29.6 - 28.8 (C-h to C- k), 28.3 (C-g), 25.0 (C-f) (only one half of Compound 3 is shown)

[0077] The structure of Compound 3 was also investigated by mass spectrometry. Main peaks were observed as expected for the M+ion at 425.3, and for the [M-Na]+adduct at 447.3. Other peaks were observed as expected.

[0078] A compound (Compound 4) was synthesised from 10-undecanal and terephthalaldehyde, as shown below:

[0079] In an oven-dried round bottom flask with a magnetic stirrer, terephthalaldehyde (TAA) (2128 mg, 15.87 mmol, 1 equiv.) was dissolved in 25 mL methanol. After complete dissolution, 1 mL NaOH (3 M) was injected and stirred for another 5 minutes, followed by the addition of 10-undecenal (UA) (5610 mg, 2.01 equiv.). While precipitate formation was already observed within an hour, the contents were allowed to stir for approx. 4 hours at room temperature. 10 mL fresh methanol was added to dilute the precipitates, which were allowed to stir for another hour (total 5 hours). The reaction flask was subsequently removed from the string and transferred to a fridge. After 5 days, the precipitates were

[0083] The structure of Compound 4 was also investigated by mass spectrometry. Main peaks were observed as expected for the {M+H}+ion at 435.3, and for the [M+Na]+adduct at 457.3. Other peaks were observed as expected.

[0084] Examples of polymers in accordance with the present invention were synthesised from Compound 3, using (i) Grubbs 2ndgeneration catalyst or (ii) Hovey da-Grubbs 2ndgeneration catalyst. The purified Compound 3 (1.80 g, 1.0 equiv) was carefully weighed into an oven-dried two-neck round bottom flask. A pre-determined amount of catalyst was added to the monomer. A vacuum-tight magnetic stirrer coupler fitted with a PTFE-coated steel stirring rod was added for mechanical stirring. The flask was connected to an overhead stirrer and a vacuum / argon line. Initially, the reaction contents were flushed with argon for ca. 15 minutes. Stirring was then initiated and the reaction was gradually heated to the desired temperature under a dynamic vacuum (1-2 mbar). Reaction was stopped by disconnecting the vacuum and removing the flask from the heating block. Once the polymer cooled down to room temperature, THF (5 mL) was added to dissolve the polymer. Ethyl vinyl ether (1.5 mL) was then added to the solution and stirred for 30 minutes to quench the reaction. Purification of polymer from the residual monomer was carried out by precipitation into cold methanol (60 mL). Purified polymer was isolated following centrifugation (3800 rpm, 8 minutes). The isolated polymer was washed with fresh methanol three times and dried on the vacuum line. GPC and DSC analysis were conducted on the purified polymer samples. For reaction conversion estimation by 1H NMR, a crude polymer sample was taken before the purification step.Table 1 - polymers produced from Compound 3 using Grubbs 2ndgeneration catalystTable 2 - polymers produced from Compound 3 using Hoveyda-Grubbs 2ndgeneration catalystTable 3 - polymer produced from Compound 4 using Hoveyda-Grubbs 2ndgeneration catalyst

[0085] The structure of the polymer was confirmed using1H NMR, 500MHz, CDCh. The measurement of Mn and Mw was performed using THF as eluent and relative to polystyrene standards. %Conversion was calculated from 'H NMR data via the disappearance of the terminal olefin signals. The yield was estimated as the mass fraction insoluble in cold methanol.

[0086] Several of the polymer examples mentioned above were characterised further using differential scanning calorimetry and thermogravimetric analysis, as shown below in Table 4.Table 4 - characteristics of certain polymer examples

[0087] Glass transition temperature Tgi, melting temperature Tmiand melting enthalpy AHmi were determined on the first heating scan in the differential scanning calorimeter. Glass transition temperature Tg2 was determined on the second heating scan. A melting transition was not observed on the second heating scan. Td-s% is the temperature at 5% weight loss, Td-50% is the temperature at 50% weight loss and Td-max is the temperature for maximum weight loss, as determined using thermogravimetric analysis (TGA) under an inert atmosphere. The residual weight is the residual weight of char recovered after TGA measurement performed under an inert atmosphere.

[0088] All chemicals were obtained from commercial sources and used without any purification unless stated. Diformylfuran (DFF) was successfully synthesized in excellent yields starting from 5-hydroxymethylfurfural (HMF) (99%) using MnCh as the oxidant with a method already described in E. M. Serum, S. Selvakumar, N. Zimmermann and M. P. Sibi, Green Chem., 2018, 20, 1448-1454. 5-hydroxymethylfurfural (HMF, 99%) was supplied by Fluorochem UK. 10-undecenal or undecylenic aldehyde (UA, 97%) was purchased from Thermo Scientific UK. MgSC was obtained from Fisher. Grubbs 2ndgeneration (M204), Hovey da-Grubbs 2ndgeneration (M720) catalysts and NaOH were all acquired from Merck. All solvents were of analytical grade and used as received.

[0089] The examples above illustrate the present invention using a furan core. Those skilled in the art will realise that other cores could be used. In this connection, a thiophene core may be incorporated by reacting thiophene dicarbaldehyde (Sigma Aldrich or AKScientific) with a suitable side-group providing aldehyde. Similarly, a pyridine core could be provide by reacting 2, 6-diformyl pyridine (Sigma Aldrich) with a suitable side-group providing aldehyde. A benzene core could be provided by reacting a benzene dicarbaldehyde (such as ortho- or meta-benzene dicarbaldehyde) with a suitable side-group forming aldehyde.

[0090] The examples above illustrate the reaction of a core-providing molecule with an unsaturated aldehyde that provides a polymerisable C=C bond in the product molecule. In the examples above, the C=C bond is located at the end of a chain. The C=C group need not be located at the end of a chain. Furthermore, those skilled in the art will realise that the present invention need not be limited to the synthesis of product molecules with unsaturated chains. Those skilled in the art will realise that saturated chains may be provided by reacting a core-providing molecule with a saturated aldehyde, such as decanal.

[0091] The examples above illustrate the reaction of a core-providing molecule with an unsaturated aldehyde that provides a polymerisable C=C bond in the product molecule. Those skilled in the art will realise that polymerisation need not involve the C=C group. For example, a polymer may be formed from an aldehyde group. Alternatively, the aldehyde group may be reduced to form an -OH group that can partake in a polymerisation reaction, for example, with a monomer comprising a carboxylic acid or acid chloride.

[0092] The examples above illustrate that synthesis of a product molecule in which there is a C=C group in a position beta to the ring, and with a C=O group beta to the C=C group. Those skilled in the art will realise that it is possible to reduce the aldehyde to a primary alcohol, for example, using a suitable reducing agent, such as NaBFU or Li AIH4. The C=C group may also be reduced to C-C using a suitable reducing agent, such as hydrogen in the presence of a suitable catalyst. A reductive amination may be performed on the aldehyde group, for example. In this connection, a primary or secondary amine may be reacted with the product molecule comprising the aldehyde group, for example, in the presence of Na(AcO)3BH, AcO, THF at room temperature. An imine may also be formed from the aldehyde group, for example, by reaction with a primary amine in mildly acidic conditions.

[0093] The examples above illustrate the synthesis of a product molecule in which there is a C=C group in a position beta to the ring, and with a C=O group beta to the C=C group.Those skilled in the art will realise that it is possible to react the C=C double bond with an epoxidation agent, such as meta-chloroperoxybenzoic acid to form an epoxy (-O-) group between the two carbon-atoms. Subsequent reaction of the epoxy group with acid would form a diol, with a hydroxyl group on each carbon atom that were previously linked by the epoxy group.

[0094] The examples above illustrate the synthesis of a polymerisable monomer that comprises polymerisable C=C groups. Those skilled in the art will realise that other polymerisable groups may be provided, such as alkyne groups, conjugated C=C groups, acid groups, alcohol groups or cyano groups.

[0095] The examples above illustrate the synthesis of symmetric product molecules by providing a single core-providing molecule and a single reactive aldehyde. Those skilled in the art would realise that this need not be the case. For example, two different aldehydes could be reacted with a single core-providing molecule, thereby providing three different product molecules, one of which is asymmetric. Alternatively, one of the aldehyde groups of the core-providing molecule may be protected, while the core-providing molecule is reacted with a first aldehyde. The protected aldehyde group may then be deprotected, facilitating reaction of the deprotected aldehyde group with a second aldehyde.

[0096] The examples above illustrate the synthesis of a homopolymer. Those skilled in the art will realise that one or more copolymers may be formed. Those skilled in the art will also realise that reaction conditions other than those mentioned above may be used.

[0097] Where in the foregoing description, integers or elements are mentioned which have known, obvious or foreseeable equivalents, then such equivalents are herein incorporated as if individually set forth. Reference should be made to the claims for determining the true scope of the present invention, which should be construed so as to encompass any such equivalents. It will also be appreciated by the reader that integers or features of the invention that are described as preferable, advantageous, convenient or the like are optional and do not limit the scope of the independent claims. Moreover, it is to be understood that such optional integers or features, whilst of possible benefit in some embodiments of the invention, may not be desirable, and may therefore be absent, in other embodiments.

Claims

CLAIMS1. A compound, Compound A, comprising (i) or (ii):where X=O, S or NR10, Y=N or CR10where R10is H or optionally substituted alkyl, each substituent optionally being selected from the group consisting of -OH, -F, -Cl, -Br, -I, and -CN, R10optionally being straight chain or branched, at least two of R1, R2, R3and R4or at least two of R5, R6, R7, R8and R9are of structure (in):(in) where, if (i) is present, the at least two of R1, R2, R3and R4may be the same or different; where, if (ii) is present, the at least two of R5, R6, R7, R8and R9may be the same or different; where A, G and M are carbon, and A is attached to the ring structure of (i) or (ii); there is a single or double carbon-carbon bond between A and G;And if there is a single bond between A and G, there may optionally also be an epoxy(-0-) group between A and G;R11is selected from the group consisting of H and optionally substituted alkyl each substituent optionally being selected from the group consisting of -OH, -F, -Cl, -Br, -I, and -CN; if there is a double bond between A and G, or if there is a single carbon-carbon-bond between A and G, and there is an epoxy group between A and G, then R12and R14are absent; if there is a single bond between A and G, and no epoxy group between A and G, then R12and R14are present and are independently selected from the group consisting of -OH, H and optionally substituted alkyl, each substituent optionally being selected from the group consisting of -OH, -F, -Cl, -Br, -I, and -CN;W is selected from the group consisting of -OH, NHR17, NR19and O, wherein if W is NR19or O, then there is a double bond between O or NR19and M; where R17and R19may be individually selected from H or optionally substituted alkyl, each substituent optionally being selected from the group consisting of -OH, -F, -Cl, -Br, -I, and -CN, wherein if W is O or NR19and if there is a double bond between the O or NR19and M, then R16is absent; wherein R15(and R16, if present) are independently selected from the group consisting of H and optionally substituted alkyl, each substituent optionally being selected from the group consisting of -OH, -F, -Cl, -Br, -I, and -CN, whereas R15may also be -OH if W is O; wherein R13is a group comprising up to 30 carbon atoms, and comprises one or more alkyl, alkenyl, cycloalkyl, aryl, alkynyl, alkanediyl, alkenediyl, cycloalkanediyl, arenediyl, alkynediyl, each of which may optionally be substituted, optionally with one or more linking groups therebetween, optionally selected from the group consisting of -S-, -O-, -O-C(O), -C(O)-O-, each substituent optionally being selected from the group consisting of -OH, -F, -Cl, -Br, -I and -CN, if (i) is present, then those of R1, R2, R3and R4not being (iii) are identical or different and are independently selected from the group consisting of H, halide or an optionally substituted alkyl group, each substituent optionally being selected from the group consisting of -OH, -F, -Cl, -Br, -I, and -CN, if (ii) is present, then those of R5, R6, R7, R8and R9not being (iii) are identical or different and are independently selected from the group consisting of H, halide, -SO3R18or an optionally substituted alkyl group, where R18is H or an optionally substituted alkyl group, each substituent optionally being selected from the group consisting of -OH, -F, -Cl, -Br, -I, and -CN.

2. The compound according to claim 1, wherein if (i) is present, then two (and only two) of R1, R2, R3and R4have the structure (iii), optionally R1and R2having the structure (iii).

3. The compound according to claim 1, wherein if (ii) is present, then two (and only two) of R5, R6, R7, R8and R9have the structure (iii), optionally R5and R9or R5and R6having the structure (iii).

4. The compound according to claim 1 or claim 2, wherein X is O.

5. The compound according to claim 1, 2 or 4, wherein those of R1, R2, R3and R4not being (iii) are optionally selected from the group consisting of H, halide and an unsubstituted alkyl group, preferably being H.

6. The compound according to claim 3, wherein those of R5, R6, R7, R8and R9not being (iii) are optionally selected from the group consisting of H, halide, -SO3R17or an unsubstituted alkyl group, preferably being H.

7. The compound according to any preceding claim, wherein R12(if present) and R14are independently selected from the group consisting of -OH, H or unsubstiuted alkyl, are optionally -OH, H or unsubstituted C1-C12 alkyl, and are optionally -OH or H.

8. The compound according to any preceding claiam wherein R11, R15and R16(if present) are independently selected from the group consisting of H or unsubstiuted alkyl, are optionally H or unsubstituted C1-C12 alkyl, and are optionally H.

9. The compound according to any preceding claim, wherein R12and R14are absent and there is either a double carbon-carbon bond between A and G or there is a single carbon-carbon bond between A and G and there is an epoxy group between A and G10. The compound according to any preceding claim, wherein R13comprises one or more moieties suitable for taking part in a polymerisation reaction, optionally selected from the group consisting of C-C double bond, C-C triple bond, conjugated CC double bond, aldehyde, amine (primary or secondary), amide, alcohol, acid, acid chloride, epoxy, acetal, ketal, hemiacetal, hemiketal, ether, ester and cyano.

11. The compound according to any preceding claim, wherein R13comprises one or more alkyl, alkenyl, alkanediyl, alkenediyl, cycloalkanediyl and cycloalkyl optionally with one or more linking groups therebetween, optionally -O-.

12. The compound according to claim 11, wherein R13comprises optionally-substituted alkyl cycloalkyl, alkyl or alkenyl, which may be linear or branched.

13. The compound according to claim 12, wherein R13comprises a C3-20 alkenyl group, optionally a C6-20 alkenyl group, optionally a Ce-15 alkenyl group and optionally a C6-12 alkenyl group, the C=C double bond being a terminal group.

14. The compound according to any preceding claim, wherein the group of structure (iii) is selected from the group consisting of structures (iv), (v), (vi), (vii), (viii), (ix), (x) and (xi):

15. The compound according to claim 14, wherein R11and R15are individually selected from H and unsubstituted C1-12 alkyl, optionally H and unsubstituted C1-6 alkyl, and are optionally both H.

16. The compound according to claim 14 or claim 15, wherein R12and R14are individually selected from -OH, H and unsubstituted C1-12 alkyl, optionally from - OH, H and unsubstituted C1-6 alkyl, and are optionally both -OH or H.

17. The compound according to any of claims 14 to 16, wherein R11, R15and R16(if present) are individually selected from H and unsubstituted C1-12 alkyl, optionally from H and unsubstituted C1-6 alkyl.

18. The compound according to any of claims 14 to 17, wherein R13comprises a C3-20 alkenyl group, optionally a C6-20 alkenyl group, optionally a Ce-15 alkenyl group and optionally a C6-12 alkenyl group.

19. A method of forming a compound in accordance with any preceding claim, the method comprising providing, in admixture, a compound of formula (xvi) or (xvii) with an aldehyde or ketone.(xvi)where X and Y are as defined in accordance with any preceding claim; where, if compound (xii) is used, then two or more, and optionally only two, of R20, R21, R22and R23are -C(O)Rn, where said two or more, and optionally said only two of R20, R21, R22and R23are the same or different; where, if compound (xiii) is used, then two or more, and optionally only two, of R24, R25, R26, R27and R28are -C(O)Rn, where said two or more, and optionally said only two of R24, R25, R26, R27and R28are the same or different.

20. The method of claim 19, wherein providing, in admixture, a compound of formula (xvi) or (xvii) with an aldehyde or ketone forms a compound of formula A comprising at least two, and optionally only two, groups of structure (iv).

21. The method of claim 20, comprising: forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (v) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv); or forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (x) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv); or forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (vii) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv); orforming a compound of Formula A comprising at least two, and optionally only two, groups of structure (viii) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv); or forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (vi) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv), comprising forming a compound of formula A comprising at least two, and optionally only two, groups of structure (x) or of structure (v) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv); or forming a compound of Formula A comprising at least two, and optionally only two, groups of structure (xi) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv), comprising forming a compound of formula A comprising at least two, and optionally only two, groups of structure (vii) or of structure (x) from a compound of formula A comprising at least two, and optionally only two, groups of structure (iv).

22. A polymer comprising a plurality of residues derived from Compound A in accordance with claims 1 to 18.

23. The polymer of claim 22, wherein the polymer is a homopolymer or copolymer.

24. The polymer of claim 22 or 23, wherein the polymer has one or more of the following properties: a Tgof at least -30°C, optionally at least -20°C, optionally at least -15°C and optionally at least -10°C; a Tgof no more than 30°C, optionally no more than 20°C, optionally no more than 15°C and optionally no more than 10°C;Mnof at least 2000 g / mol, optionally at least 3000 g / mol and optionally at least 4000g / mol;Mnof no more than 40000 g / mol, optionally no more than 35000 g / mol, optionally no more than 30000 g / mol and optionally no more than 25000 g / mol;Mwof at least 3000 g / mol, optionally at least 4000 g / mol and optionally at least 5000g / mol;Mwof no more than 80000 g / mol, optionally no more than 70000 g / mol, optionally no more than 60000 g / mol and optionally on more than 50000 g / mol; a polydispersity index (Mw / Mn) of at least 1.0, optionally at least 1.2 and optionally at least 1.4; and a polydispersity index (Mw / Mn) of no more than 5.0, optionally no more than 4.0 and optionally no more than 3.0.

25. The polymer of claims 22 to 24 comprising a plurality of residues of Compound A, wherein Compound A comprises at least one group (and optionally two groups) of structure (iv), (v), (vi), (vii), (viii), (ix), (x), (xi), (xii), (xiii), (xiv) and (xv).

26. A method of making a polymer, the method comprising polymerising Compound A according to claims 1 to 18.

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