Modified polysaccharides

Abstract

The present invention relates to modified polysaccharides, such as modified cellulose fibres and / or cellulosic fabric, and methods of making the same. The present invention also relates to uses of the modified polysaccharides, such as modified cellulose fibres and / or cellulosic fabrics.

Description

[0001] MODIFIED POLYSACCHARIDES

[0002] TECHNICAL FIELD

[0003] The present invention relates to modified polysaccharides, such as modified cellulose fibres and / or modified cellulosic fabric, and methods of making the same. The present invention also relates to uses of the modified polysaccharides, such as modified cellulose fibres and / or modified cellulosic fibres.

[0004] BACKGROUND

[0005] Cellulose is a natural polymer of P(1 — >4) linked D-glucose units, of length varying from a few hundred to several thousand pyranose rings. Cellulose is an attractive ‘green material’ due to its intrinsic mechanical and chemical properties. There is an increasing demand for introducing active agents on textile materials such as cellulose fibres and cellulosic fabrics by chemical means in order to create additional properties, i.e. , functional cellulose-based textiles.

[0006] It is known that cellulose can be modified to alter the hydrophobicity of the cellulose. The resulting modified cellulose has potential application in the packaging, textiles and biomedical industries. Altering the hydrophobicity of cellulose involves modifying the surface properties of cellulose to make the cellulose less (or more) prone to water absorption. This may be achieved through various methods, such as chemical treatment, surface coatings, or the incorporation of additives.

[0007] For example, chemical treatments, such as acylation or etherification, can introduce hydrophobic groups onto the cellulose and thereby reduce its affinity for water molecules. Surface coatings, such as polymer coatings or wax treatments, can create a barrier that prevents water from interacting with the cellulose surface. Incorporation of hydrophobic additives, such as silicone-based compounds or fluorinated materials, can further enhance the water-repellent properties of cellulose.

[0008] WO 2019 / 180449 and WO2023 / 118811 teaches that cellulose fibres and / or cellulosic fabrics which have been modified using one or more hydrocarbon chains, for example one or more hydrocarbon acids, can be used as reinforcing fibres in composite materials. The composite materials so formed were found to have good durability, good water resistance and good structural strength and engineering performance. Thus, whilst functional cellulose-based textiles are known in the art, there remains a need for further advancements in the development of functional cellulose-based textiles.

[0009] The present invention is based on our surprising finding the cellulose fibres and / or cellulosic fabrics that have been modified using one or more compound(s) of formula (II) have improved resistance to water uptake. In addition to improving the resistance of water uptake for cellulose fibres and cellulosic fabrics, it is expected that modification of other polysaccharides (e.g., chitosan) with one or more compound(s) of formula (XXI) would also improve the resistance of such polysaccharides to water uptake.

[0010] SUMMARY OF INVENTION

[0011] According to a first aspect of the present invention, there is provided a compound of formula (XX): wherein:

[0012] Ring Z is a 5- or 6-membered heteroaromatic ring containing from 1 to 4 nitrogen atoms;

[0013] A is the polysaccharide;

[0014] X is hydrogen, halogen, hydroxy, A, M or an electron-withdrawing functional group, for example, X is hydrogen, halogen, A or M;

[0015] M is ORa; a is 1 ; m is 1 ; x is 0 to 3, wherein a+m+x does not exceed the total number of substituents possible on heteroaromatic ring Z; wherein Rais Ce-Cso alkyl, Ce-Cso alkenyl, Ce-Cso alkylcarbonyl, Ce-Cso alkenylcarbonyl, CH2CH(ORc)(CH2ORd), or CH(Re)(Rf); wherein each of Rcand Rd are independently selected from hydrogen, Z", Ce-Cso alkyl, Ce-Cso alkenyl, Ce-Cso alkylcarbonyl, C6-C30 alkenylcarbonyl, or P(O)(OCi-C3alkyl)2wherein Reis C1-C10 alkyl; wherein Rfis (CH2)o(CH=CH)p(CH2)qC(O)O(Ri); wherein Ring Z' is a 5- or 6-membered heteroaromatic ring containing 1 to 4 nitrogen atoms; wherein each of Rgand Rh are independently hydrogen, halogen, hydroxy, A or M; wherein g and h are integers from 1 to 4 and g+h does not exceed the total number of substituents possible on heteroaromatic ring Z'; wherein Rj is hydrogen o is 1 to 8; p is 0 or 1 ; q is 1 to 8 wherein each of Rj and Rk are independently hydrogen, C6-C30 alkyl, C6-C30 alkenyl, Ce- Cso alkyl carbonyl, or Ce-Cso alkenylcarbonyl.

[0016] According to a second aspect of the present invention, there is provided cellulose fibres and / or cellulosic fabric of formula (I): wherein:

[0017] A is the cellulose fibres and / or cellulose fabric;

[0018] X is hydrogen, halogen, hydroxy, A or M;

[0019] M is ORa; wherein Rais Ce-Cso alkyl, Ce-Cso alkenyl, Ce-Cso alkylcarbonyl, Ce-Cso alkenylcarbonyl,

[0020] CH2CH(ORc)(CH2ORd), or CH(Re)(Rf); wherein each of Rcand Rd are independently selected from hydrogen, , Ce-

[0021] Cso alkyl, C6-C30 alkenyl, C6-C30 alkylcarbonyl, or C6-C30 alkenylcarbonyl; wherein Reis C1-C10 alkyl; wherein Rfis (CH2)o(CH=CH)p(CH2)qC(O)O(Ri) wherein each of Rgand Rh are independently hydrogen, halogen, hydroxy, A or M; wherein Rj is hydrogen o is 1 to 8;

[0022] P is 0 or 1 ; q is 1 to 8 wherein each of Rj and Rk are independently hydrogen, C6-C30 alkyl, C6-C30 alkenyl, Ce- C30 alkylcarbonyl, or C6-C30 alkenylcarbonyl.

[0023] According to a third aspect of the present invention, there is provided use of polysaccharides, such as cellulose fibres and / or cellulosic fabric, according to the first aspect or second aspect for improving resistance to water uptake.

[0024] According to a fourth aspect of the present invention, there is provided a method for preparing a polysaccharide according to the first aspect, the method comprising the step of reacting a polysaccharide with one or more compound(s) of formula (XXI): wherein X, A, M, Ra, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Ri, o, p, q, r, s, t, m and x are as defined herein; and wherein Y is a leaving group and y is at least 1 .

[0025] According to this aspect of the present invention, there is provided a method for preparing the cellulose fibres and / or cellulosic fabric according to the second aspect, the method comprising the step of reacting cellulose fibres and / or cellulosic fabric with one or more compound(s) of formula (II): wherein X, A, M, Ra, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Ri, o, p, q, r, s and t are as defined herein.

[0026] According to a fifth aspect of the present invention, there is provided an article of manufacture formed at least in part of polysaccharide according to the first aspect. According to this aspect of the present invention, there is provided an article of manufacture formed at least in part of cellulose fibres and / or cellulosic fabric according to the second aspect.

[0027] According to a sixth aspect of the present invention, there is provided a composite material comprising modified polysaccharide, wherein the modified polysaccharide is according to the first aspect. According to seventh aspect of the present invention, there is provided a composite material comprising modified cellulose fibres and / or modified cellulosic fabric, wherein the modified cellulose fibres and / or modified cellulosic fabric is according to the second aspect.

[0028] According to a eighth aspect of the present invention, there is provided an article of manufacture formed at least in part of a composite material according to the sixth or seventh aspect.

[0029] DESCRIPTION OF INVENTION

[0030] The present invention will be described in detail with reference to the Examples and accompanying drawings.

[0031] Figure 1 shows a repeating unit of cellulose.

[0032] Figure 2 shows (A) a scanning electron microscopy (SEM) image and (B) the distribution of fibre widths for a modified hemp fabric. Figure 3 shows (A) a SEM image and (B) the distribution of fibre widths for a modified flax fabric.

[0033] Figure 4 shows the % water uptake values after immersion in water for three untreated hemp fabrics and a hemp fabric treated according to the method of Example 1 .

[0034] Figure 5 shows the % water uptake values after immersion in water for three untreated flax fabrics and a flax fabric treated according to the method of Example 1.

[0035] Figure 6 shows the % water uptake values after immersion in water for three untreated felt fabrics and a felt fabric treated according to the method of Example 1.

[0036] The term “about” is used herein to denote that the numerical value is not strictly limiting, and the skilled person will understand that the value may extend above or below (as appropriate) the exact value in line with the skilled person’s understanding of the value. For example, the term “about” may signify a value that is up to ±10% of the value.

[0037] The term “halogen” as used herein refers to fluorine, chlorine, bromine or iodine.

[0038] The term “hydroxy” as used herein refers to -OH.

[0039] The term “alkyl” as used herein refers to a linear or branched hydrocarbon chain connected to the rest of the molecule by a single bond. The alkyl group may be defined by the number of carbon atoms in the hydrocarbon chain. For example, the expression “C1-C30 alkyl” means that the linear or branched hydrocarbon chain has 1 to 30 carbon atoms. For example, the alkyl may comprise, 6 to 30 carbon atoms (labelled as C6-C30), 8 to 26 carbon atoms (labelled as “C8-C26”), 10 to 24 carbon atoms (labelled as “C10- C24”) or 12 to 22 carbon atoms (labelled as “C12-C22”). The alkyl group may be optionally substituted.

[0040] The term “alkenyl” as used herein refers to a linear or branched hydrocarbon chain having one or more carbon-carbon double bonds. The alkenyl group may be defined by the number of carbon atoms in the hydrocarbon chain. For example, the expression “C6-C30 alkenyl” means that the linear or branched hydrocarbon chain has 6 to 30 carbon atoms. The alkenyl groups may be optionally substituted. The term “alkynyl” as used herein refers to a linear or branched hydrocarbon chain having one or more carbon-carbon triple bonds. The alkynyl group may be defined by the number of carbon atoms in the hydrocarbon chain. For example, the alkynyl group may have 1 to 30 carbon atoms (labelled as C1-C30), 1 to 20 carbon atoms (labelled as C1-C20), 1 to 15 carbon atoms (labelled as C1-C15) or 1 to 10 carbon atoms (labelled as C1-C10). The alkynyl group may be optionally substituted.

[0041] The term “cycloalkyl” as used herein refers to a saturated or unsaturated cyclic, bicyclic or bridged bicyclic hydrocarbon group of 3 to 12 carbon atoms or 3 to 8 carbon atoms.

[0042] The term “heterocyclyl” as used herein refers to a saturated or unsaturated 3-, 4-, 5-, 6- , or 7-membered ring containing one, two or three heteroatoms independently selected from nitrogen, oxygen and sulfur.

[0043] The term “alkoxy” as used herein refers to the group -O-alkyl wherein the alkyl is an optionally substituted C1-C30 alkyl, C1-C20 alkyl, C1-C15 alkyl, or C1-C10 alkyl.

[0044] The term “carboxy” as used herein refers to the group -C(O)OH.

[0045] The term “amino” as used herein refers to the group -NH2, -NH(Rm), -N(Rm)2, - N(Rm)(Rm’). For example, Rmand Rm’ may independently be selected from an optionally substituted alkyl (such as an optionally substituted C1-C30 alkyl, C1-C20 alkyl, C1-C15 alkyl or Ci-C alkyl), alkenyl, alkynyl, cycloalkyl, aryl, or heteroaryl group. For the avoidance of any doubt, when the amino is -N(Rm)(Rm’) then Rmand Rm’ are different.

[0046] The term “ester” as used herein refers to the group -C(O)ORnwhere Rnis an alkyl, alkenyl or alkynyl group. The alkyl is an optionally substituted C1-C30 alkyl, C1-C20 alkyl, C1-C15 alkyl or C1-C10 alkyl. The alkenyl is an optionally substituted C1-C30 alkenyl, C1- C20 alkenyl, C1-C15 alkenyl or C1-C10 alkenyl. The alkynyl group is an optionally substituted C1-C30 alkynyl, C1-C20 alkynyl, C1-C15 alkynyl or C1-C10 alkynyl.

[0047] The term “epoxy” as used herein refers to a three-membered cyclic ether. The epoxy group contains an oxygen atom attached to two adjacent carbon atoms of the hydrocarbon chain. The term “alkylcarbonyl” as used herein refers to the group -C(O)alkyl. The alkyl is defined herein. For example, the alkyl may be an optionally substituted Ce-Cso alkyl, Cs- C26 alkyl, C10-C24 alkyl or C12-C22 alkyl.

[0048] The term “alkenylcarbonyl” as used herein refers to the group -C(O)alkenyl. The alkenyl is defined herein. For example, the alkenyl may be an optionally substituted Ce- C30 alkenyl, C8-C26 alkenyl, C10-C24 alkenyl or C12-C22 alkenyl.

[0049] The term “haloalkyl” as used herein refers to an alkyl group substituted with one or more halogen atoms.

[0050] The term “haloalkenyl” as used herein refers to an alkenyl group substituted with one or more halogen atoms.

[0051] The term “haloalkynyl” as used herein refers to an alkynyl group substituted with one or more halogen atoms.

[0052] The term “haloalkoxy” as used refers to the group -O-alkyl wherein the alkyl group is substituted with one or more halogen atoms.

[0053] The term “aryl” as used herein refers to a mono-, bi-, or other multi-carbocyclic, aromatic ring system. The aryl group can be optionally fused to one or more rings selected from aryls, cycloalkyls, and heterocyclyls. The aryl group may be optionally substituted. For example, aryl groups include, but are not limited to, monocyclic aromatic ring systems, wherein the ring comprises 6 carbon atoms.

[0054] The term “heteroaryl” as used herein refers to a mono-, bi-, or multi cyclic, aromatic ring system containing one or more heteroatoms, for example one to three heteroatoms, such as nitrogen, oxygen, and sulfur. The heteroaryl group can be optionally fused to one or more aromatic or non-aromatic rings. The heteroaryl group may be optional substituted. For example, heteroaryl groups include, but are not limited to, monocyclic aromatic ring systems, wherein the ring comprises 2 to 5 carbon atoms and 1 to 3 heteroatoms.

[0055] The term “carbonyl” as used herein refers to the group -C(O)Rowhere Rois an optionally substituted alkyl, alkenyl, alkynyl, aryl or heteroaryl. The term “carboxy” as used herein refers to the group -C(O)OH.

[0056] The term “carboxamido” as used herein refers to the group -NHC(O)RPwhere Rpis an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl or heteroaryl.

[0057] The term “cyano” as used herein refers to the group -CN.

[0058] The term “isocyano” as used herein refers to the group -NC.

[0059] The term “amido” as used herein refers to the group -C(O)NH2, -C(O)NHRq, or - C(O)N(Rq)(Rq’) where Rqand Rq’ are independently selected from an optionally substituted alkyl, alkynyl, alkenyl, cycloalkyl, heterocyclyl, aryl or heteroaryl. For the avoidance of any doubt, when the amido is -C(O)N(Rq)(Rq’) then Rqand Rq’ are different.

[0060] The term “azide” as used herein refers to the group -N3.

[0061] The term “nitro” as used herein refers to the group -NO2.

[0062] The term “thiol” as used herein refers to the group -SH.

[0063] The term “alkylthiol” as used herein refers to the group -Salkyl.

[0064] The term “arylthiol” as used herein refers to the group -Saryl.

[0065] The term “phosphate” as used herein refers to the group -OP(O)(ORr)2, or - OP(O)(ORr)(ORr’), where Rrand Rr’ are independently selected from an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl and hydrogen.

[0066] The term “phosphite” as used herein refers to the group -OP(O)(ORr)H, where Rris as defined above.

[0067] The term “phosphonate” as used herein refers to the group -OP(O)(ORr)(Rr’), where Rrand Rr’ are as defined above. The term “phosphinate” as used herein refers to the group -OP(O)(Rr)(Rr’), where Rrand Rr’ are as defined above.

[0068] The term “sulfonate” as used herein refers to the group -OS(O)2(ORs), where Rsis selected from an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl and hydrogen.

[0069] The term “nitrate” as used herein refers to the group -ONO2.

[0070] The term “nitrite” as used herein refers to the group -ONO.

[0071] The term “imine” as used herein refers to the group -C(Rt)=NRt’, where Rtand Rt’ are independently selected from an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl and hydrogen.

[0072] The term “nitrone” as used herein refers to the group -N(O)=C(Rt)(Rt’), or - C(Rt)=N(O)(Rt’), where Rtand Rt’ are as defined above.

[0073] The term “diazo” as used herein refers to the group -C(Rt)=N2, where Rtis as defined above.

[0074] The term “diazonium” as used herein refers to the group -N2+Y; where Y is an anionic counterion including, but not limited to, halides, sulfates and phosphates.

[0075] The term “sulfone” as used herein refers to the group -S(O)2Ru, where Ruis selected from an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl and hydrogen.

[0076] The term “sulfoxide” as used herein refers to the group -S(O)RV, where Rvis selected from an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl and hydrogen.

[0077] The term “disulfide” as used herein refers to the group -S-SRW, where Rwis selected from an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl and hydrogen. The term “thioester” as used herein refers to the group -C(O)SRXor -C(S)ORX, wherein Rxis selected from an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl and hydrogen.

[0078] The term “thioether” as used herein refers to the group -SRZ, wherein Rzis selected from an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl.

[0079] Modified polysaccharide such as cellulose fibres and / or cellulosic fabric

[0080] Modified using one or more compound(s) of formula (XXI), such as formula (II) The present invention is based on our surprising finding that polysaccharides, in particular cellulose fibres and / or cellulosic fabrics, that have been modified using one or more compound(s) of formula (XXI), for example, formula (II), have improved resistance to water uptake. There is provided herein a polysaccharide compound of formula ( wherein:

[0081] Ring Z is a 5- or 6-membered heteroaromatic ring containing from 1 to 4 nitrogen atoms;

[0082] A is the polysaccharide;

[0083] X is hydrogen, halogen, hydroxy, A, M, or an electron-withdrawing functional group, optionally, wherein X is hydrogen, halogen, A or M;

[0084] M is ORa; a is 1 ; m is 1 ; x is 0 to 3, wherein a+m+x does not exceed the total number of substituents possible on heteroaromatic ring Z; wherein Rais Ce-Cso alkyl, Ce-Cso alkenyl, Ce-Cso alkylcarbonyl, Ce-Cso alkenylcarbonyl, CH2CH(ORc)(CH2ORd), or CH(Re)(Rf); wherein each of Rcand Rd are independently selected from hydrogen, Z", Ce-Cso alkyl, Ce-Cso alkenyl, C6-C30 alkylcarbonyl, C6-C30 alkenylcarbonyll, or P(O)(OCi-C3alkyl)2; wherein Reis C1-C10 alkyl; wherein Rfis (CH2)o(CH=CH)p(CH2)qC(O)O(Ri) wherein Ring Z' is a 5- or 6-membered heteroaromatic ring containing 1 to 4 nitrogen atoms; wherein each of Rgand Rh are independently hydrogen, halogen, hydroxy, A or M; wherein g and h are integers from 1 to 4 and g+h does not exceed the total number of substituents possible on heteroaromatic Ring Z'; wherein Rj is hydrogen o is 1 to 8; p is 0 or 1 ; q is 1 to 8 wherein each of Rj and Rk are independently hydrogen, C6-C30 alkyl, C6-C30 alkenyl, Ce- C30 alkyl carbonyl, or C6-C30 alkenylcarbonyl.

[0085] There is also provided herein cellulose fibres and / or cellulosic fabric of formula (I): wherein:

[0086] A is the cellulose fibres and / or cellulose fabric;

[0087] X is hydrogen, halogen, hydroxy, A or M;

[0088] M is ORa; wherein Rais C6-C30 alkyl, C6-C30 alkenyl, C6-C30 alkylcarbonyl, C6-C30 alkenylcarbonyl, CH2CH(ORc)(CH2ORd), or CH(Re)(Rf); wherein each of Rcand Rd are independently selected from hydrogen, , Ce- C30 alkyl, C6-C30 alkenyl, C6-C30 alkylcarbonyl, or C6-C30 alkenylcarbonyl; wherein Reis C1-C10 alkyl; wherein Rfis (CH2)o(CH=CH)p(CH2)qC(O)O(Ri) wherein each of Rgand Rh are independently hydrogen, halogen, hydroxy, A or M; wherein Rj is hydrogen o is 1 to 8; p is 0 or 1 ; q is 1 to 8 wherein each of Rj and Rk are independently hydrogen, C6-C30 alkyl, C6-C30 alkenyl, Ce- C30 alkyl carbonyl, or C6-C30 alkenylcarbonyl.

[0089] In the present invention, A is a polysaccharide. In some examples, A is a linear polysaccharide. In some examples, A is a natural or unnatural polysaccharide. In some examples, A is a (1-4)beta-glycosylic polymer. In some examples, A is selected from cellulose, chitosan, starch, glycogen or a combination thereof. The polysaccharide is preferably cellulose.

[0090] In some examples, the polysaccharide is a polysaccharide-based nonwoven, polysaccharide-based woven fabric, a polysaccharide-based film, or a polysaccharide- based composite material. In some examples, the polysaccharide is a cellulose- containing material, such as a cellulose film, cellulose fibres or cellulosic fabric. In some examples, the cellulose-containing material is a crystalline cellulose material, an amorphous cellulose or a combination thereof.

[0091] In some examples, the cellulose is cellulose microfibrils or cellulose macrofibrils. In some examples, the cellulose is cellulose fibres and / or cellulosic fabric. In some examples, the cellulose fibres and / or cellulosic fabric is selected from cellulose yarn, cellulose nonwovens or cellulose wovens. In some examples, the cellulose nonwoven is paper. In the present invention, A is cellulose fibres and / or cellulosic fabric. In some examples, A is cellulosic fabric, for example woven cellulosic fabric.

[0092] In some examples, Ring Z is a 5- or 6-membered heteroaromatic ring containing from 1 to 4 nitrogen atoms. In some examples, Ring Z is a 5-membered heteroaromatic ring containing 2 or 3 nitrogen atoms. In some examples, Ring Z is a 6-membered heteroaromatic ring containing 1, 2, 3 or 4 nitrogen atoms. In some examples, Ring Z is a 6-membered heteroaromatic ring containing 3 nitrogen atoms, that is, a triazine. In some examples, Ring Z is selected from: some examples, Ring Preferably Ring Z is 1,3,5-triazine.

[0093] In some examples, Ring Z' is the same as or different from Ring Z. In some examples, Ring Z' is identical to Ring Z. In some examples, Ring Z' is a 5-membered heteroaromatic ring containing 2 or 3 nitrogen atoms. In some examples, Ring Z' is a 6- membered heteroaromatic ring containing 1, 2, 3 or 4 nitrogen atoms. In some examples, Ring Z' is a 6-membered heteroaromatic ring containing 3 nitrogen atoms, that is, a triazine. In some examples, Ring Z' is selected from:

[0094] In some examples, Ring Z and Ring Z' are independently selected from: some examples, Ring Ring Preferably, Ring Z is 1 ,3,5-triazine and Ring Z' is 1 ,3,5-triazine.

[0095] In some examples, there is provided herein a polysaccharide of formula (XX): wherein:

[0096] Ring Z is selected from:

[0097] A is the polysaccharide;

[0098] X is hydrogen, halogen, hydroxy, A, M or an electron-withdrawing functional group, optionally, X is hydrogen, halogen, A or M;

[0099] M is ORa; a is 1 ; m is 1 ; x is 0 to 3, wherein a+m+x does not exceed the total number of substituents possible on heteroaromatic ring Z; wherein Rais C6-C30 alkyl, C6-C30 alkenyl, C6-C30 alkylcarbonyl, C6-C30 alkenylcarbonyl, CH2CH(ORc)(CH2ORd), or CH(Re)(Rf); wherein each of Rcand Rd are independently selected from hydrogen, Z", C6-C30 alkyl, C6-C30 alkenyl, C6-C30 alkylcarbonyl, C6-C30 alkenylcarbonyll, or P(O)(OCi-C3alkyl)2; wherein Reis C1-C10 alkyl; wherein Rfis (CH2)o(CH=CH)p(CH2)qC(O)O(Ri) wherein each of Rgand Rh are independently hydrogen, halogen, hydroxy, A or M; wherein g and h are integers from 1 to 4 and g+h does not exceed the total number of substituents possible on heteroaromatic Ring Z'; wherein Rj is hydrogen o is 1 to 8; p is 0 or 1 ; q is 1 to 8 wherein each of Rj and Rk are independently hydrogen, Ce-Cso alkyl, Ce-Cso alkenyl, Ce- C30 alkyl carbonyl, or C6-C30 alkenylcarbonyl.

[0100] In some examples, a+m+x is the number of atoms in the heteroaromatic ring minus the number of nitrogen atoms in the heteroaromatic ring. In some examples, Ring Z is a 6- membered heteroaromatic ring and a+m+x is 6 minus the number of nitrogen atoms in the heteroaromatic ring. In some examples, Ring Z is a 5-membered heteroaromatic ring and a+m+x is 5 minus the number of nitrogen atoms in the heteroaromatic ring.

[0101] In some examples, g+h is the number of atoms in the heteroaromatic ring minus 1 minus the number of nitrogen atoms in the heteroaromatic ring. In some examples, Ring Z’ is a 6-membered heteroaromatic ring and g+h is 5 minus the number of nitrogen atoms in the heteroaromatic ring (i.e. , (6-1) minus the number of nitrogen atoms in the heteroaromatic ring). In some examples, Ring Z’ is a 5-membered heteroaromatic ring and g+h is 4 minus the number of nitrogen atoms in the heteroaromatic ring (i.e., (5-1) minus the number of nitrogen atoms in the heteroaromatic ring).

[0102] In some examples, there is provided herein a polysaccharide of formula (XX): wherein:

[0103] Ring Z is selected from:

[0104] A is the polysaccharide;

[0105] X is hydrogen, halogen, hydroxy, A, M or an electron-withdrawing functional group, optionally, X is hydrogen, halogen, A or M;

[0106] M is ORa; m is 1 , a is 1 ; x is 1 ; a+m+x is 3 (i.e., 6-3=3) wherein Rais Ce-Cso alkyl, Ce-Cso alkenyl, Ce-Cso alkylcarbonyl, Ce-Cso alkenylcarbonyl, CH2CH(ORc)(CH2ORd), or CH(Re)(Rf); wherein each of Rcand Rd are independently selected from hydrogen, Z', Ce-Cso alkyl, Ce-Cso alkenyl, C6-C30 alkylcarbonyl, C6-C30 alkenylcarbonyll, or P(O)(OCi-C3alkyl)2; wherein Reis C1-C10 alkyl; wherein Rfis (CH2)o(CH=CH)p(CH2)qC(O)O(Ri) wherein each of Rgand Rh are independently hydrogen, halogen, hydroxy, A or M; wherein g and h are integers from 1 to 2 and g+h is 2 (i.e. , 6-1-3=2); wherein Rj is hydrogen o is 1 to 8; p is 0 or 1 ; q is 1 to 8 wherein each of Rj and Rk are independently hydrogen, Ce-Cso alkyl, Ce-Cso alkenyl, Ce- C30 alkyl carbonyl, or C6-C30 alkenylcarbonyl.

[0107] In preferred examples, formula (XX) is a polysaccharide modified by one or more of compound(s) of formula (XXI), for example, formula (II). In another preferred example, formula (XX) is a polysaccharide modified by one of more of compound(s) of formula (II).

[0108] In preferred embodiments, formula (XX) is formula (I).

[0109] In the present invention, the modified polysaccharide contains at least one M and at least one A. In some examples, the modified polysaccharide contains M, A and X.

[0110] In the present invention, X is hydrogen, halogen, hydroxy, A, M or an electronwithdrawing functional group. In the present invention, X is hydrogen, halogen, hydroxy, A or M. For example, X may be hydrogen, fluoride, chloride, bromide, iodide, hydroxy, A or M. For example, X may be hydrogen, chloride, hydroxy, A or M. In some examples, X is selected from chloride, hydroxy, or M. In certain examples, X is chloride. The electron-withdrawing functional group may be selected from nitro, cyano, fluoro, chloro, trifluoromethyl functional groups.

[0111] In the present invention, M is ORa, wherein Rais C6-C30 alkyl, C6-C30 alkenyl, C6-C30 alkylcarbonyl, C6-C30 alkenylcarbonyl, CH2CH(ORc)(CH2ORd), or CH(Re)(Rf).

[0112] In some examples, M is ORaand Rais C6-C30 alkyl. For example, Ramay be a C6-C30 alkyl, C8-C26 alkyl, C10-C24 alkyl or C12-C22 alkyl, wherein the C6-C30 alkyl, C8-C26 alkyl, C10-C24 alkyl or C12-C22 alkyl is optionally substituted with one or more of alkynyl, cycloalkyl, heterocyclyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heteroaryl, alkoxy, epoxy, haloalkoxy, carbonyl, carboxy, carboxamido, cyano, isocyano, halogen, hydroxy, amino, amido, azide, nitro, nitrate, nitrite, nitrone, diazo, diazonium, imine, phosphate, phosphite, phosphonate, phosphinate, thiol, alkylthio, arylthiol, sulfonate, sulfone, sulfoxide, disulfide, thioether or thioester.

[0113] In certain examples, M is ORaand Rais C12-C22 alkyl. For example, the C12-C22 alkyl may be selected from dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl, nonadecyl, arachidyl, heneicosyl, behenyl, 9,10-epoxypalmityl and 9,10- epoxyoctadecyl. In particular examples, the C12-C22 alkyl is selected from stearyl and 9,10-epoxyoctadecyl.

[0114] In some examples, M is ORaand Rais C6-C30 alkenyl. For example, Ramay be a Ce- C30 alkenyl, C8-C26 alkenyl, C10-C24 alkenyl or C12-C22 alkenyl, wherein C6-C30 alkenyl, C8-C26 alkenyl, C10-C24 alkenyl or C12-C22 alkenyl is optionally substituted with one or more of alkynyl, cycloalkyl, heterocyclyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heteroaryl, alkoxy, epoxy, haloalkoxy, carbonyl, carboxy, carboxamido, cyano, isocyano, halogen, hydroxy, amino, amido, azide, nitro, nitrate, nitrite, nitrone, diazo, diazonium, imine, phosphate, phosphite, phosphonate, phosphinate, thiol, alkylthio, arylthiol, sulfonate, sulfone, sulfoxide, disulfide, thioether or thioester.

[0115] In certain examples, M is ORaand Rais C12-C22 alkenyl. For example, the C12-C22 alkenyl may be selected from palmitoleyl, olelyl and erucyl. In particular examples, the C12-C22 alkenyl may be olelyl.

[0116] In some examples, M is ORaand Rais C6-C30 alkylcarbonyl or C6-C30 alkenylcarbonyl. For example, Ramay be a Ce-Cso alkylcarbonyl, C8-C26 alkylcarbonyl, C10-C24 alkylcarbonyl or C12-C22 alkylcarbonyl, wherein the C6-C30 alkylcarbonyl, C8-C26 alkylcarbonyl, C10-C24 alkylcarbonyl or Ci2-C22 alkylcarbonyl is optionally substituted with one or more of alkynyl, cycloalkyl, heterocyclyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heteroaryl, alkoxy, epoxy, haloalkoxy, carbonyl, carboxy, carboxamido, cyano, isocyano, halogen, hydroxy, amino, amido, azide, nitro, nitrate, nitrite, nitrone, diazo, diazonium, imine, phosphate, phosphite, phosphonate, phosphinate, thiol, alkylthio, arylthiol, sulfonate, sulfone, sulfoxide, disulfide, thioether or thioester.

[0117] For example, Ramay be a C6-C30 alkenylcarbonyl, C8-C26 alkenylcarbonyl, C10-C24 alkenylcarbonyl or C12-C22 alkenylcarbonyl, wherein the C6-C30 alkenylcarbonyl, C8-C26 alkenylcarbonyl, C10-C24 alkenylcarbonyl or Ci2-C22 alkenylcarbonyl is optionally substituted with one or more of alkynyl, cycloalkyl, heterocyclyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heteroaryl, alkoxy, epoxy, haloalkoxy, carbonyl, carboxy, carboxamido, cyano, isocyano, halogen, hydroxy, amino, amido, azide, nitro, nitrate, nitrite, nitrone, diazo, diazonium, imine, phosphate, phosphite, phosphonate, phosphinate, thiol, alkylthio, arylthiol, sulfonate, sulfone, sulfoxide, disulfide, thioether or thioester.

[0118] In certain examples, M is ORaand Rais a C12-C22 alkylcarbonyl or C12-C22 alkenylcarbonyl selected from dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, icosanoyl, docosanoyl, (9Z)-tetradec-9-enoyl, (9Z)-hexdec-9-enoyl, (6Z)-hexadec-6- enoyl, (9Z)-octadec-9-enoyl, (E)-octadec-9-enoyl, (11E)-octadec-11-enoyl, (9Z,12Z)- octadec-9, 12-dienoyl, (9E, 12E)-octadeca-9, 12-dienoyl, (9Z, 12Z, 15Z)-octadeca- 9, 12, 15-trienoyl, (5Z,8Z,11Z,14Z)-icosa-5,8,11 ,14-tetraenoyl, (5Z,8Z,11Z,14Z,17Z)- icosa-5,8,11 ,14,17-pentanoyl, (13Z)-docos-13-enoyl and (4Z,7Z,10Z,13Z,16Z,19Z)- docosa-4,7,10,13,16,19-hexaenoyl. In particular examples, the C12-C22 alkylcarbonyl or C12-C22 alkenyl carbonyl is selected from octadecanoyl and (9Z)-octadec-9-enoyl.

[0119] In some examples, M is ORaand Rais CH2CH(ORc)(CH2ORd), wherein each of Rcand Rd are independently selected from hydrogen, Z", C6-C30 alkyl, C6-C30 alkenyl, C6-C30 alkylcarbonyl, or C6-C30 alkenylcarbonyl, and wherein each of Rgand Rh are independently hydrogen, halogen, hydroxy, A or M. In some examples, M is ORaand Rais CH2CH(ORc)(CH2ORd), wherein each of Rcand Rd are independently selected from hydrogen, Z", C6-C30 alkyl, C6-C30 alkenyl, C6-C30 alkylcarbonyl, or C6-C30 alkenylcarbonyl, and wherein each of Rgand Rh are independently hydrogen, halogen, hydroxy, A or M; and wherein Ring Z' in Z" is identical to Ring Z. In some examples, M is ORaand Rais CH2CH(ORc)(CH2ORd), wherein each of Rcand Rd are independently selected from hydrogen, , Ce-Cso alkyl, Ce-Cso alkenyl, Ce-Cso alkylcarbonyl, or Ce-Cso alkenylcarbonyl, and wherein each of Rgand Rh are independently hydrogen, halogen, hydroxy, A or M. In some examples, Ring

[0120] Rais CH2CH(ORc)(CH2ORd), wherein each of Rcand Rd are independently selected from hydrogen, , C6-C30 alkyl, C6-C30 alkenyl, C6-C30 alkylcarbonyl, or C6-C30 alkenylcarbonyl, and wherein each of Rgand Rh are independently hydrogen, halogen, hydroxy, A or M.

[0121] In some examples, M is ORaand Rais CH2CH(ORc)(CH2ORd), wherein Rcis Z", Rd is C6-C30 alkylcarbonyl or C6-C30 alkenylcarbonyl, and each of Rgand Rh are independently hydrogen, chloride, hydroxy, A or M. In some examples, M is ORaand Rais CH2CH(ORc)(CH2ORd), wherein Rcis Z", Rd is C6-C30 alkylcarbonyl or C6-C30 alkenylcarbonyl, and each of Rgand Rh are independently hydrogen, chloride, hydroxy, A or M; and wherein Ring Z' in Z" is identical to Ring Z. In certain examples, M is ORaand Rais CH2CH(ORc)(CH2ORd), wherein alkylcarbonyl or C6-C30 alkenylcarbonyl, and each of Rgand Rh are independently hydrogen, chloride, hydroxy, A or M. In certain examples, Ring CH2CH(ORc)(CH2ORd), wherein Cso alkylcarbonyl or Ce-Cso alkenylcarbonyl, and each of Rgand Rh are independently hydrogen, chloride, hydroxy, A or M.

[0122] For example, Rdmay be a Ce-Cso alkylcarbonyl, C8-C26 alkylcarbonyl, C10-C24 alkylcarbonyl or C12-C22 alkylcarbonyl, wherein the C6-C30 alkylcarbonyl, C8-C26 alkylcarbonyl, C10-C24 alkylcarbonyl or Ci2-C22 alkylcarbonyl is optionally substituted with one or more of alkynyl, cycloalkyl, heterocyclyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heteroaryl, alkoxy, epoxy, haloalkoxy, carbonyl, carboxy, carboxamido, cyano, isocyano, halogen, hydroxy, amino, amido, azide, nitro, nitrate, nitrite, nitrone, diazo, diazonium, imine, phosphate, phosphite, phosphonate, phosphinate, thiol, alkylthio, arylthiol, sulfonate, sulfone, sulfoxide, disulfide, thioether or thioester.

[0123] For example, Rdmay be a C6-C30 alkenylcarbonyl, C8-C26 alkenylcarbonyl, C10-C24 alkenylcarbonyl or C12-C22 alkenylcarbonyl, wherein the C6-C30 alkenylcarbonyl, C8-C26 alkenylcarbonyl, C10-C24 alkenylcarbonyl or Ci2-C22 alkenylcarbonyl is optionally substituted with one or more of alkynyl, cycloalkyl, heterocyclyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heteroaryl, alkoxy, epoxy, haloalkoxy, carbonyl, carboxy, carboxamido, cyano, isocyano, halogen, hydroxy, amino, amido, azide, nitro, nitrate, nitrite, nitrone, diazo, diazonium, imine, phosphate, phosphite, phosphonate, phosphinate, thiol, alkylthio, arylthiol, sulfonate, sulfone, sulfoxide, disulfide, thioether or thioester.

[0124] In some examples, M is ORaand Rais CH2CH(ORc)(CH2ORd), wherein Rcis Z", Rdis C12-C22 alkylcarbonyl or C12-C22 alkenyl carbonyl, and Rgand Rh are both chlorine. In more certain examples, M is ORaand Rais CH2CH(ORc)(CH2ORd), wherein Rcis , Rdis C12-C22 alkylcarbonyl or C12-C22 alkenyl carbonyl, and Rgand Rh are both chlorine. In some examples, Ring

[0125] CH2CH(ORc)(CH2ORd), wherein alkylcarbonyl or C12-C22 alkenyl carbonyl, and Rgand Rh are both chlorine. For example, Rd may be a C12-C22 alkylcarbonyl or C12-C22 alkenylcarbonyl selected from dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, icosanoyl, docosanoyl (9Z)-tetradec-9-enoyl, (9Z)- hexdec-9-enoyl, (6Z)-hexadec-6-enoyl, (9Z)-octadec-9-enoyl, (E)-octadec-9-enoyl, (11E)-octadec-11-enoyl, (9Z,12Z)-octadec-9,12-dienoyl, (9E,12E)-octadeca-9,12- dienoyl, (9Z, 12Z, 15Z)-octadeca-9, 12,15-tri enoyl , (5Z,8Z, 11 Z, 14Z)-icosa-5,8, 11 ,14- tetraenoyl, (5Z,8Z, 11 Z, 14Z, 17Z)-icosa-5,8, 11 ,14,17-pentanoyl, (13Z)-docos-13-enoyl and (4Z,7Z,10Z,13Z,16Z,19Z)-docosa-4,7,10,13,16,19-hexaenoyl. In particular examples, the C12-C22 alkylcarbonyl or Ci2-C22 alkenyl carbonyl is selected from octadecanoyl and (9Z)-octadec-9-enoyl.

[0126] In certain examples, M is ORaand Rais CH2CH(ORc)(CH2ORd), wherein Rcis C6-C30 alkylcarbonyl or C6-C30 alkenylcarbonyl, Rd is Z" and each of Rgand Rh are independently hydrogen, chloride, hydroxy, A or M. In certain examples, M is ORaand Rais CH2CH(ORc)(CH2ORd), wherein Rcis C6-C30 alkylcarbonyl or C6-C30 alkenylcarbonyl, Rd is Z" and each of Rgand Rh are independently hydrogen, chloride, hydroxy, A or M; wherein Ring Z' of Z" is identical to Ring Z. In certain examples, M is ORaand Rais CH2CH(ORc)(CH2ORd), wherein Rcis C6-C30 alkylcarbonyl or C6-C30 alkenylcarbonyl, each of Rgand Rh are independently hydrogen, chloride, hydroxy, A or M. In certain examples, Ring and Rais CH2CH(ORc)(CH2ORd), wherein Rcis Ce-Cso alkylcarbonyl or Ce-Cso alkenylcarbonyl, each of Rgand Rh are independently hydrogen, chloride, hydroxy, A or M.

[0127] For example, Rcmay be a C6-C30 alkylcarbonyl, C8-C26 alkylcarbonyl, C10-C24 alkylcarbonyl or C12-C22 alkylcarbonyl, wherein the C6-C30 alkylcarbonyl, C8-C26 alkylcarbonyl, C10-C24 alkylcarbonyl or Ci2-C22 alkylcarbonyl is optionally substituted with one or more of alkynyl, cycloalkyl, heterocyclyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heteroaryl, alkoxy, epoxy, haloalkoxy, carbonyl, carboxy, carboxamido, cyano, isocyano, halogen, hydroxy, amino, amido, azide, nitro, nitrate, nitrite, nitrone, diazo, diazonium, imine, phosphate, phosphite, phosphonate, phosphinate, thiol, alkylthio, arylthiol, sulfonate, sulfone, sulfoxide, disulfide, thioether or thioester.

[0128] For example, Rcmay be a C6-C30 alkenylcarbonyl, C8-C26 alkenylcarbonyl, C10-C24 alkenylcarbonyl or C12-C22 alkenylcarbonyl, wherein the C6-C30 alkenylcarbonyl, C8-C26 alkenylcarbonyl, C10-C24 alkenylcarbonyl or Ci2-C22 alkenylcarbonyl is optionally substituted with one or more of alkynyl, cycloalkyl, heterocyclyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heteroaryl, alkoxy, epoxy, haloalkoxy, carbonyl, carboxy, carboxamido, cyano, isocyano, halogen, hydroxy, amino, amido, azide, nitro, nitrate, nitrite, nitrone, diazo, diazonium, imine, phosphate, phosphite, phosphonate, phosphinate, thiol, alkylthio, arylthiol, sulfonate, sulfone, sulfoxide, disulfide, thioether or thioester.

[0129] In certain examples, M is ORaand Rais CH2CH(ORc)(CH2ORd), wherein Rcis C12-C22 alkylcarbonyl or C12-C22 alkenyl carbonyl, Rd is Z" and Rgand Rh are both chlorine. In certain examples, M is ORaand Rais CH2CH(ORc)(CH2ORd), wherein Rcis C12-C22 alkylcarbonyl or C12-C22 alkenyl carbonyl, Rd is Z" and Rgand Rh are both chlorine; and Ring Z' in Z" is identical to Ring Z. In certain examples, M is ORaand Rais CH2CH(ORc)(CH2ORd), wherein Rcis C12-C22 alkylcarbonyl or C12-C22 alkenyl carbonyl, are both chlorine. In certain examples, Ring Z is wherein Rcis C12-C22 alkylcarbonyl or C12-C22 alkenyl carbonyl, are both chlorine. For example, Rcmay be a C12-C22 alkylcarbonyl or C12-C22 alkenylcarbonyl selected from dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, icosanoyl, docosanoyl, (9Z)-tetradec-9-enoyl, (9Z)-hexdec-9-enoyl, (6Z)-hexadec-6-enoyl, (9Z)- octadec-9-enoyl, (E)-octadec-9-enoyl, (11E)-octadec-11-enoyl, (9Z,12Z)-octadec-9,12- dienoyl, (9E, 12E)-octadeca-9, 12-dienoyl, (9Z, 12Z, 15Z)-octadeca-9, 12,15-tri enoy I , (5Z,8Z, 11 Z, 14Z)-icosa-5,8, 11 , 14-tetraenoyl, (5Z,8Z, 11 Z, 14Z, 17Z)-icosa-5,8, 11 ,14,17- pentanoyl, (13Z)-docos-13-enoyl and (4Z,7Z,10Z,13Z,16Z,19Z)-docosa-

[0130] 4,7,10,13,16,19-hexaenoyl. In particular examples, the C12-C22 alkylcarbonyl or C12-C22 alkenyl carbonyl is selected from octadecanoyl and (9Z)-octadec-9-enoyl.

[0131] In certain examples, M is 0Raand Rais CH2CH(ORc)(CH2ORd), wherein each of Rcand Rd are independently Ce-Cso alkylcarbonyl or Ce-Cso alkenylcarbonyl. For example, each of Rcand Rd may independently be a C12-C22 alkylcarbonyl or C12-C22 alkenylcarbonyl selected from dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, icosanoyl, docosanoyl, (9Z)-tetradec-9-enoyl, (9Z)-hexdec-9-enoyl, (6Z)-hexadec-6- enoyl, (9Z)-octadec-9-enoyl, (E)-octadec-9-enoyl, (11E)-octadec-11-enoyl, (9Z,12Z)- octadec-9, 12-dienoyl, (9E, 12E)-octadeca-9, 12-dienoyl, (9Z, 12Z, 15Z)-octadeca- 9, 12, 15-trienoyl, (5Z,8Z,11Z,14Z)-icosa-5,8,11 ,14-tetraenoyl, (5Z,8Z,11Z,14Z,17Z)- icosa-5,8,11 ,14,17-pentanoyl, (13Z)-docos-13-enoyl and (4Z,7Z,10Z,13Z,16Z,19Z)- docosa-4,7,10,13,16,19-hexaenoyl. In particular examples, the C12-C22 alkylcarbonyl or C12-C22 alkenyl carbonyl is selected from octadecanoyl and (9Z)-octadec-9-enoyl.

[0132] In some examples, M is ORaand Rais CH(Re)(Rf), wherein Reis C1-C10 alkyl and Rf is

[0133] ORj ^ “°Rk(CH2)o(CH=CH)p(CH2)qC(O)O(Rj), wherein Rj is hydrogen or , wherein o is 1 to 8, p is 0 or 1 , and q is 1 to 8, and wherein each of Rj and Rk are independently hydrogen, C6-C30 alkyl, C6-C30 alkenyl, C6-C30 alkylcarbonyl, or C6-C30 alkenylcarbonyl. In certain examples, M is ORaand Rais CH(Re)(Rf), wherein Reis C3-C6 alkyl and Rf is (CH2)o(CH=CH)p(CH2)qC(O)O(Rj), wherein Rj is hydrogen, wherein o is 1 to 4, p is 0 or 1 and q is 3 to 8.

[0134] In more certain examples, M is ORaand Rais CH(Re)(Rf), wherein Reis C5 alkyl and Rf is (CH2)o(CH=CH)p(CH2)qC(O)O(Rj), wherein Rj is hydrogen, wherein o is 1 , p is 1 and q is 8.

[0135] In certain examples, M is ORaand Rais CH(Re)(Rf), wherein Reis C3-C6 alkyl and Rf is (CH2)o(CH=CH)p(CH2)qC(O)O(Rj), wherein , wherein o is 1 to 4, p is 0 or 1 and q is 3 to 8, wherein each of Rj and Rk are independently C6-C30 alkyl, C6-C30 alkenyl, C6-C30 alkyl carbonyl, or Ce-Cso alkenylcarbonyl. For example, each of Rj and Rk may be a C12-C22 alkylcarbonyl, or C12-C22 alkenylcarbonyl, wherein the C12-C22 alkylcarbonyl, or C12-C22 alkenylcarbonyl is optionally substituted with one or more of alkynyl, cycloalkyl, heterocyclyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heteroaryl, alkoxy, epoxy, haloalkoxy, carbonyl, carboxy, carboxamido, cyano, isocyano, halogen, hydroxy, amino, amido, azide, nitro, nitrate, nitrite, nitrone, diazo, diazonium, imine, phosphate, phosphite, phosphonate, phosphinate, thiol, alkylthio, arylthiol, sulfonate, sulfone, sulfoxide, disulfide, thioether or thioester.

[0136] In more certain examples, M is ORaand Rais CH(Re)(Rf), wherein Reis C5 alkyl and Rf O j

[0137] ^ “oRkis (CH2)o(CH=CH)p(CH2)qC(O)O(Rj), wherein Rj is '« , wherein o is 1 , p is 1 and q is 8, wherein each of Rj and Rk are independently C12-C22 alkylcarbonyl, or C12- C22 alkenylcarbonyl. In particular examples, each of Rj and Rk are independently a C12- C22 alkylcarbonyl or C12-C22 alkenylcarbonyl selected from dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, icosanoyl, docosanoyl, (9Z)-tetradec-9-enoyl, (9Z)- hexdec-9-enoyl, (6Z)-hexadec-6-enoyl, (9Z)-octadec-9-enoyl, (E)-octadec-9-enoyl, (11E)-octadec-11-enoyl, (9Z,12Z)-octadec-9,12-dienoyl, (9E,12E)-octadeca-9,12- dienoyl, (9Z, 12Z, 15Z)-octadeca-9, 12,15-tri enoyl , (5Z,8Z, 11 Z, 14Z)-icosa-5,8, 11 ,14- tetraenoyl, (5Z,8Z, 11 Z, 14Z, 17Z)-icosa-5,8, 11 ,14,17-pentanoyl, (13Z)-docos-13-enoyl and (4Z,7Z, 10Z, 13Z, 16Z, 19Z)-docosa-4,7, 10,13,16,19-hexaenoyl. In other examples, M is ORaand Rais CH(Re)(Rf), wherein Reis C5 alkyl and Rf is

[0138] ORj

[0139] J- °Rk(CH2)o(CH=CH)p(CH2)qC(O)O(Rj), wherein Rj is , wherein o is 1 , p is 1 and q is 8, wherein each of Rj and Rkare -C(O)(CH2)r(CH=CH)sCH2CH(ORi)(CH2)tCH3, wherein r is 1 to 8, s is 0 or 1 and t is 1 to 4, and wherein Ri is Z" and Rgand Rh are as defined above. In other more certain examples, M is ORaand Rais CH(Re)(Rf), wherein

[0140] Reis Cs alkyl and Rf is (CH2)o(CH=CH)p(CH2)qC(O)O(Rj), wherein wherein o is 1 , p is 1 and q is 8, wherein each of Rj and Rkare - C(O)(CH2)r(CH=CH)sCH2CH(ORi)(CH2)tCH3, wherein r is 1 to 8, s is 0 or 1 and t is 1 to 4, and wherein Ri is Z" and Rgand Rh are as defined above; and wherein Ring Z' of Z" is identical to Ring Z. In other more certain examples, M is ORaand Rais CH(Re)(Rf), wherein Reis C5 alkyl and Rf is (CH2)o(CH=CH)p(CH2)qC(O)O(Rj), wherein Rj is , wherein o is 1 , p is 1 and q is 8, wherein each of Rj and Rkare - C(O)(CH2)r(CH=CH)sCH2CH(ORi)(CH2)tCH3, wherein r is 1 to 8, s is 0 or 1 and t is 1 to

[0141] 4, and wherein are as defined above. In particular examples, r is 8, s is 1 and t is 4, and Rgis A and Rh is chlorine. In other more certain examples, Ring wherein Reis Cs alkyl and Rf is (CH2)o(CH=CH)p(CH2)qC(O)O(Rj), wherein , wherein o is

[0142] 1 , p is 1 and q is 8, wherein each of Rj and Rkare -

[0143] C(O)(CH2)r(CH=CH)sCH2CH(ORi)(CH2)tCH3, wherein r is 1 to 8, s is 0 or 1 and t is 1 to 4, and wherein are as defined above. In particular examples, r is 8, s is 1 and t is 4, and Rgis A and Rh is chlorine. In other particular examples, r is 8, s is 1 and t is 4, and both Rgand Rh are chlorine. In some examples, the one or more compound(s) of formula (I) is / are selected from:

[0144]

[0145] These modified polysaccharides advantageously provide improved resistance to water uptake. The polysaccharides may be further advantageous in that they may be biomaterials, may be recyclable and bioavailable, and may have a relatively low cost and low weight. These modified cellulose fibres and / or modified cellulosic fabric advantageously provide improved resistance to water uptake. The modified cellulose fibres and / or cellulosic fabric may be further advantageous in that they may be biomaterials, may be recyclable and bioavailable, and may have a relatively low cost and low weight.

[0146] Bonding between polysaccharides (e.g., cellulose) and compound(s) of formula (XXI), (e.g., formula (II))

[0147] The polysaccharides may have been modified by covalently linking the one or more compound(s) of formula (XXI) (e.g., formula (II)) to the polysaccharide. For example, the polysaccharide may have been modified to covalently link the one or more compound(s) of formula (XXI) (e.g., formula (II)) to the polysaccharide by any suitable attachment functionality. The one or more compound(s) of formula (XXI) (e.g., formula (II)) may be covalently linked to the polysaccharide by bonding with one or more of the OH groups present on the sugar units of the polysaccharide. In some examples, the modification covalently links the one or more compound(s) of formula (XXI) (e.g., formula (II)) to the polysaccharide via an ether linkage (R-O-R’).

[0148] In some examples, the cellulose may have been modified by covalently linking the one or more compound(s) of formula (XXI) (e.g., formula (II)) to the cellulose. For example, the cellulose may have been modified to covalently link the one or more compound(s) of formula (XXI) (e.g., formula (II)) to the cellulose by any suitable attachment functionality. The one or more compound(s) of formula (XXI) (e.g., formula (II)) may be covalently linked to the cellulose by bonding with one or more of the OH groups present on the sugar units of the cellulose. In some examples, the modification covalently links the one or more compound(s) of formula (XXI) (e.g., formula (II)) to the cellulose via an ether linkage (R-O-R’).

[0149] The cellulose fibres and / or cellulosic fabrics may have been modified by covalently link the one or more compound(s) of formula (II) to the cellulose fibres and / or cellulosic fabric. For example, the cellulose fibres and / cellulosic fabric may have been modified to covalently link the one or more compound(s) of formula (II) to the cellulose fibres and / or cellulosic fabric by any suitable attachment functionality. The one or more compound(s) of formula (II) may be covalently linked to the cellulose fibres and / or cellulosic fabric by bonding with one or more of the OH groups present on the sugar units of the cellulose fibres and / or cellulosic fabric. In some examples, the modification covalently links the one or more compound of formula (II) to the cellulose fibres and / or cellulosic fabric via an ether linkage (R-O-R’). Cellulose

[0150] Cellulose is a natural polymer of P(1 — >4) linked D-glucose units, of length varying from a few hundred to several thousand pyranose rings. Figure 1 shows the repeating unit of cellulose. There are three reactive hydroxy groups in each glucose. Two consecutive glucose units are rotated at an angle of 180° in the plane from each other, due to the bond angle preferences of the bridging acetal (O-C-O) moieties, so that a single unit of the polymer consists of two glucose rings. The chain has an extensive hydrogen bonding network between the ring and side-chain hydroxyl groups both in the chain and between adjacent chains, giving stiffness and hence a degree of crystallinity to the polymer. As a consequence, solid state cellulose contains both amorphous (low order) and crystalline (high order) regions.

[0151] Cellulose chain length varies with the source. From wood pulp the length ranges from 300 to 1700 repeating units. Plant fibres, such as cotton, are 800 to 10,000 units. Microcrystalline celluloses of 150 to 300 units are prepared by chemical partial chain degradation of longer cellulose polymers.

[0152] The three hydroxyl groups present on each glucose component of the polymer are each able to undergo alkylation and acylation reactions using standard chemical reaction conditions. For example, methylcellulose can be prepared readily by treatment of an aqueous suspension of cellulose in water with sodium hydroxide, followed by addition of chloromethane or dimethyl sulfate. It is commercially available in a number of different degrees of methylation and chain length.

[0153] Cellulose may, for example, be extracted or obtained from plants and / or macroorganisms and / or microorganisms such as tunicates or bacteria using methods known to those skilled in the art. For example, cellulose may be extracted from one or more of flax, cotton, hemp, coir, jute, manila and wood pulp. Cellulose may be extracted by prehydrolysis with mineral acids or alkali followed by pulping (e.g. using NaOH), followed by bleaching (e.g. using sodium chlorite, hydrogen peroxide or ozone). Cellulose may also be obtained from commercial sources.

[0154] The cellulose used in the present invention may be used in any suitable form including, but not limited to, powders, films, short fibers, yarns, mats, felts, woven or knitted fabrics. In some examples, the cellulose used in the present invention may be used in any suitable form including, but not limited to, powders, short fibers, yarns, mats, felts, woven or knitted fabrics.

[0155] The cellulose fibres used to prepare the modified cellulose fibres described herein may, for example, be in the form of a fabric (cellulosic fabric). The term “fabric” refers to a material wherein a plurality of cellulose fibres are interlaced together, for example by weaving, knitting, knotting, felting, spreading, crocheting, looping, braiding, lacing, bonding or any other suitable methods. In some examples, the fabric is a woven fabric. The fabric may, for example, have a weight ranging from about 10gsm to about 1000gsm, for example from about 50gsm to about 500gsm, for example from about 100gsm to about 450gsm, for example from about 200gsm to about 400gsm. The fabric may, for example, comprise one or more different fibres in addition to the one or more cellulose fibres. For example, the fabric may comprise one or more polymer fibres, for example one or more polypropylene fibres, and / or one or more hemicellulose fibres and / or one or more lignin fibres in addition to the one or more cellulose fibres.

[0156] The cellulose fibres (e.g. the cellulose fibres used to make the cellulosic fabric) may, for example, have an average width equal to or greater than about 10 nm, for example equal to or greater than about 20 nm, for example equal to or greater than about 30 nm. For example, the cellulose fibres (e.g. the cellulose fibres used to make the cellulosic fabric) may have an average width equal to or less than about 100 nm or equal to or less than about 75 nm or equal to or less than about 50 nm. The average width of the cellulose fibres may be measured by X-ray diffraction (XRD).

[0157] The cellulose fibres may, for example, be derived from any suitable source. For example, the cellulose fibres may be derived from a natural source or may be manmade. For example, the cellulose may be derived from cotton, jute, flax, hemp, ramie, sisal, coconut husk, bamboo or a combination of one or more thereof. For example, the cellulose fibres may be man-made rayon fibres.

[0158] In some examples, the cellulose fibres used to prepare the modified cellulose fibres described herein may be woven flax or hemp fibres (a flax or hemp fibre cellulosic fabric), which may, for example, be commercially available. Chitosan

[0159] Chitosan is a linear polysaccharide composed of randomly distributed P(1 — >4) linked D- glucosamine and / V-acetyl-D-glucosamine units, of length varying from a few hundred to several thousand pyranose rings. Chitosan fibers vary from 1.5 to 10 kilodaltons. There are two reactive hydroxy groups in each glucosamine. Two consecutive glucosamine / / V-acetylglucosamine units are rotated at an angle of 180° in the plane from each other, due to the bond angle preferences of the bridging acetal (O-C-O) moieties, so that a single unit of the polymer consists of two glucosamine / A / - acetylglucosamine rings. The chain has an extensive hydrogen bonding network both in the chain and between adjacent chains, giving stiffness and hence a degree of crystallinity to the polymer. As a consequence, solid state chitosan contains both amorphous (low order) and crystalline (high order) regions.

[0160] Chitosan chain length varies with the source. Chitosan is derived by treating chitin (or a source of chitin) with an alkaline substance, such as sodium hydroxide. Chitin can be extracted from, for example, the shells of crabs, shrimp, shellfish and lobsters. The chitin fibres may, for example, be derived from any suitable source. For example, the chitin fibres may be derived from a natural source or may be manmade. For example, the chitin may be derived from the shells of crabs, shrimp, shellfish and lobsters. For example, the chitin fibres may be man-made chitin fibres.

[0161] The chitosan used in the present invention may be used in any suitable form, including but not limited to powders, films, short fibres, yarns, mats, felts, woven or knitted fabrics. The chitosan used to prepare the modified chitosan described herein may be in the form of chitosan fibres or a chitosan fabric. The term “chitosan fabric” may refer to a material wherein a plurality of chitosan fibres are interlaced together, for example, by weaving, knitting, knotting, felting, spreading, crocheting, looping, braiding, lacing, bonding or any other suitable methods. In some examples, the fabric is a woven fabric. The fabric may, for example, have a weight ranging from about 10gsm to about 1500gsm, for example from about 50gsm to about 1250gsm, for example from about 100gsm to about 1000gsm, for example from about 200gsm to about 400gsmThe fabric may, for example, comprise one or more different fibres in addition to the one or more chitosan fibres. For example, the fabric may comprise one or more polymer fibres, for example one or more polypropylene fibres, and / or one or more chitin fibres, and / or one or more cellulose fibres, and / or one or more hemicellulose fibres and / or one or more lignin fibres in addition to the one or more chitosan fibres.

[0162] The chitosan fibres (e.g. the chitosan fibres used to make the chitosan fabric) may, for example, have an average width of from about 1 pm to about 1000 pm, for example, about 50 pm to about 900 pm, about 100 pm to about 850 pm, about 150 pm to about 800 pm, about 200 pm to about 750 pm, about 250 pm to about 700 pm, about 300 pm to about 650 pm, or about 350 pm to about 500 pm. The average width of the chitosan fibres may be measured by X-ray diffraction (XRD).

[0163] The chitosan fibres may, for example, be derived from any suitable source. For example, the chitosan fibres may be derived from a natural source of chitin or may be manmade. For example, the chitin may be derived from the shells of crabs, shrimp, shellfish and lobsters. For example, the chitosan fibres may be man-made chitin fibres.

[0164] Method(s) of preparing the modified polysaccharide (e.g., the modified cellulose fibres and / or cellulosic fabric)

[0165] There is provided a method for preparing the modified polysaccharide of formula (XX) as described herein, the method comprising the step of reacting a polysaccharide with one or more compound(s) of formula (XXI): wherein X, A, M, Ra, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Ri, o, p, q, r, s, t, m and x are as defined herein; and wherein Y is a leaving group, y is at least 1 , and m+x+y does not exceed the total number of substituents possible on heteroaromatic ring Z.

[0166] The method may be a nucleophilic aromatic substitution reaction in which Y is the leaving group and the polysaccharide is the nucleophile. The method may be a nucleophilic aromatic substitution reaction in which Y is the leaving group and a hydroxyl functional group of the polysaccharide is the nucleophile. In some examples, Y may be selected from halogen, hydroxy, alkoxy (e.g., methoxy, ethoxy or propoxy), tosylate (i.e., OTs, wherein Ts is toluenesulfonyl), mesylate (i.e., OMs, wherein Ms is methanesulfonyl), nitro, sulfonate, phosphonate, phosphinate, and phosphate. In some examples, Y is selected halogen, alkoxy, tosylate, or mesylate. In some examples, Y is a halogen. In some examples, Y is chlorine.

[0167] In some examples, X is the same as or different from Y. In some examples, X is identical to Y. In some examples, X is selected from halogen and hydrogen, and Y is halogen. In some examples, X is selected from hydrogen, halogen, hydroxy, A, M or an electron-withdrawing functional group and Y is a leaving group, for example, a halogen. In some examples, X and Y are each independently halogen. In some examples, X and Y are chlorine.

[0168] In some examples, Z is a 6-membered heteroaromatic ring, m is 1, y is 1 to 4 and x is 0 to 3, wherein m+x+y does not exceed the total number of substituents possible on heteroaromatic ring Z. In some examples, Z is a 5-membered heteroaromatic ring, m is 1 , y is 1 to 3 and x is 0 to 2, wherein m+x+y does not exceed the total number of substituents possible on heteroaromatic ring Z. In some examples, Z is a 6-membered heteroaromatic ring, m is 1 , y is 1 and x is 0 to 3, wherein m+x+y does not exceed the total number of substituents possible on heteroaromatic ring Z. In some examples, Z is a 5-membered heteroaromatic ring, m is 1, y is 1 and x is 0 to 2, wherein m+x+y does not exceed the total number of substituents possible on heteroaromatic ring Z.

[0169] In some examples, halogen, x is 1 , X is selected from halogen, M or A (for example, X is selected from halogen or M), and m is 1. In some examples, halogen, x is 1 , X is selected from halogen,

[0170] M or A (for example, X is selected from halogen or M), and m is 1 , wherein if X is halogen, the halogen is the same as or different from Y (for example, X is the same halogen as Y). In some examples, chlorine, x is 1 , X is selected from chlorine, M or A, and m is 1. In some examples,

[0171] Y is chlorine, x is 1 , X is selected from chlorine or M (for example, chlorine), and m is 1.

[0172] In some examples, the method may be a method for preparing a modified polysaccharide of formula (XX) as described herein, the method comprising the step of reacting polysaccharide (for example, cellulose fibres and / or cellulosic fabric) with one or more compound(s) of formula (Ila): wherein Y, X, A, M, Ra, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Ri, o, p, q, r, s and t are as defined herein. In some examples, Y is halogen, for example, fluorine, chlorine, bromine or iodine. In some examples, Y is chlorine. In some examples, Y is the same as or different from X.

[0173] The method may be a method for preparing cellulose fibres and / or cellulosic fabric of formula (I) as described herein, the method comprising the step of reacting cellulose fibres and / or cellulosic fabric with one or more compound(s) of formula (Ila):

[0174] wherein Y, X, A, M, Ra, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Ri, o, p, q, r, s and t are as defined herein.

[0175] There is provided a method for preparing cellulose fibres and / or cellulosic fabric modified with one or more compound(s) of formula (I) as described herein, the method comprising the step of reacting cellulose fibres and / or cellulosic fabric with one or more compound(s) of formula (II): wherein X, A, M, Ra, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Ri, o, p, q, r, s and t are as defined herein.

[0176] Method(s) of modification

[0177] The polysaccharide may be modified by any suitable method known to those skilled in the art. For example, the one or more compounds of formula (XXI) (e.g., formula (II)) may be linked (for example covalently linked) to the polysaccharide backbone by any suitable method known to those skilled in the art. The cellulose fibres and / or cellulosic fabric may be modified by any suitable method known to those skilled in the art. For example, the one or more compounds of formula (II) may be linked (for example covalently linked) to the cellulosic sugar backbone by any suitable method known to those skilled in the art.

[0178] The modification may be achieved via chemical bond between the polysaccharide and compound of formula (XXI) (e.g., formula (II)). For example, the modification may be achieved via a SNAr reaction between polysaccharide alcohol (of the polysaccharide) and the leaving group-carbon (e.g., the halogen-carbon) of the one or more compound(s) of formula (XXI). The modification may be achieved via chemical bond between the cellulose and compound of formula (II). For example, the modification may be achieved via a SNAr reaction between cellulosic alcohol (of the cellulose fibres and / or cellulosic fabric) and the leaving group-carbon (e.g., the halogen-carbon) of the one or more compound(s) of formula (II). For example, the modification may be achieved via a SNAr reaction between cellulosic alcohol (of the cellulose fibres and / or cellulosic fabric) and the chlorine-carbon of the one or more compound(s) of formula (II).

[0179] The method may be performed in the presence of a suitable base. Suitable bases include, but are not limited to sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.

[0180] The method may, for example, involve a heterogenous method, for example on solid polysaccharide in a solvent containing the one or more compound(s) of formula (XXI) (e.g., formula (II)) and a suitable base. The method may, for example, involve a heterogenous method, for example on solid cellulose fibres and / or cellulosic fabric in a solvent containing the one or more compound(s) of formula (XXI) and a suitable base. The method may, for example, involve a heterogenous method, for example on solid cellulose fibres and / or cellulosic fabric in a solvent containing the one or more compound(s) of formula (II) and a suitable base.

[0181] Suitable bases that may be used in the method of the present invention include, but are not limited to sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.

[0182] The solvent may be an aqueous solvent (such as water) or organic solvent (such as acetone, ethanol, ethyl acetate, hexanes, or pentanes). For example, the one or more compounds of formula (XXI) may be applied to the polysaccharide (e.g., cellulose fibres and / or cellulosic fabric) in an aqueous solvent, an aqueous emulsion or an organic solvent. For example, the one or more compounds of formula (II) may be applied to the cellulose fibres and / or cellulosic fabric in an aqueous solvent, an aqueous emulsion or an organic solvent.

[0183] In some examples, the solvent is an aqueous solvent (such as water). In such cases, it may be necessary to use an emulsifier. Suitable emulsifiers include, but are not limited to, anionic emulsifiers such as N-lauryl sarcosine sodium salt, neutral emulsifiers such as an ethylene oxide I propylene oxide block copolymer (commercially available examples include, but are not limited to, Synperonic® F108a and Pluronic® F127), or a combination of anionic and neutral emulsifiers.

[0184] The method may involve heating the mixture of polysaccharide in the presence of the one or more compound(s) of formula (XXI) and the suitable base. The method may involve heating the mixture of cellulose fibres and / or cellulosic fabric in the presence of the one or more compound(s) of formula (XXI) and the suitable base. The method may involve heating the mixture of polysaccharide in the presence of the one or more compound(s) of formula (II) and the suitable base. The method may involve heating the mixture of cellulose fibres and / or cellulosic fabric in the presence of the one or more compound(s) of formula (II) and the suitable base.

[0185] The mixture may be heated to for example at least about 30 °C, for example at least about 50 °C, for example at least about 80 °C, for example at least about 100 °C, or for example at least about 110 °C. The mixture may be heated to for example, no more than about 250 °C, for example no more than about 220 °C, for example no more than about 200 °C, for example no more than about 180 °C, or for example no more than about 150 °C. In some examples, the mixture is heated from about 30 °C to about 250 °C, from about 50 °C to about 220 °C, from about 80 °C to about 200 °C, from about 100 °C to about 180 °C, or from about 110 °C to about 150 °C.

[0186] The mixture may be heated at the above temperatures for at least about 10 minutes, for at least about 20 minutes, for at least about 30 minutes, for at least about 1 hour, or for at least about 2 hours.

[0187] After modifying the polysaccharide in the solvent, the modified polysaccharide may be removed from the solvent. For example, the modified polysaccharide may be obtained by filtering the reaction mixture. After modifying the cellulose fibres and / or cellulosic fabric in the solvent, the modified cellulose fibres and / or modified cellulosic fabric may be removed from the solvent. For example, the modified cellulose fibres and / or modified cellulosic fabric may be obtained by filtering the reaction mixture.

[0188] The obtained modified polysaccharide may then be washed (for example in excess solvent such as acetone) and / or be dried (such as at room temperature or elevated temperatures to remove excess solvent). Additionally, the modified polysaccharide may be oven cured. The obtained modified cellulose fibres and / or modified cellulosic fabric may then be washed (for example in excess solvent such as acetone) and / or be dried (such as at room temperature or elevated temperatures to remove excess solvent). Additionally, the modified cellulose fibres and / or modified cellulosic fabric may be oven cured.

[0189] The polysaccharide prior to modification may be untreated or pretreated in an alkaline solution. The pre-treated polysaccharide may then be dried (for example in an oven) or used damp (for example having been passed through a mangle). The cellulose fibres and / or cellulosic fabric prior to modification may be untreated or pretreated in an alkaline solution. The pre-treated cellulose fibres and / or cellulosic fabric may then be dried (for example in an oven) or used damp (for example having been passed through a mangle).

[0190] X-ray powder diffraction (XRD) may be used to analyse the crystalline structure of the polysaccharide. X-ray powder diffraction (XRD) may be used to analyse the crystalline structure of the cellulose fabric. For example, the % crystallinity, crystallite size, and interplanar distance can be measured.

[0191] The “degree of substitution” refers to the % of monomer units (e.g. anhydroglycose units in cellulose) having a compound of formula (XX) (e.g., formula (I)) attached. The modified polysaccharide (e.g., the modified cellulose fibres and / or modified cellulosic fabric) may, for example, have a degree of substitution of at least about 0.1 %, for example at least about 0.5 % or at least about 1 %. For example, the polysaccharide (e.g., the cellulose fibres and / or cellulosic fabric) may have a degree of substitution ranging from about 0.1 % to about 100 %, for example from about 0.1 % to about 60 % or from about 0.1 % to about 50 % or from about 0.1 % to about 40 % or from about 0.1 % to about 30 % or from about 0.1 % to about 20 % or from about 0.1 % to about 15 % or from about 0.1 % to about 10 %.

[0192] Preparation of the compound of formula (XXI) (e.g., formula (ID)

[0193] The compound of formula (XXI) may be prepared using any suitable method known to the person skilled in the art. In some examples, the compound of formula (XXI) may be prepared by reacting the presence of a suitable base with or without a solvent, wherein y is 1 to 5 and x is 0 to 4 and x+y does not exceed the total number of substituents possible on heteroaromatic ring Z. In some examples, y is 1 and the method produces a compound in which Y has been replaced by M. In some examples, y is greater than 1 and the method produces a compound in which each Y has been replaced by M (that is, ORa). In some examples, the reaction is an SNAr reaction and both X and Y are susceptible to nucleophilic aromatic substitution but only Y is substituted by M in the process.

[0194] In some examples, the compound of formula (XXI) may be prepared by reacting the presence of a suitable base in the absence of solvent, wherein y is 2 to 5 and x is 0 to 4 and x+y does not exceed the total number of substituents possible on heteroaromatic ring Z. In some examples, each Y is the same or different.

[0195] The compound of formula (II) may be prepared using any suitable method known to the person skilled in the art. For example, the compound of formula (II) may be prepared by reacting cyanuric halide with HORain the presence of a suitable base with or without a solvent. In some examples, the compound of formula (II) is prepared by reacting cyanuric halide with HORain the presence of a suitable base and in the absence of solvent. For example, the compound of formula (II) may be prepared by reacting cyanuric chloride with HORain the presence of a suitable base with or without a solvent. In some examples, the compound of formula (II) is prepared by reacting cyanuric chloride with HORain the presence of a suitable base and in the absence of solvent. Intermediate for use in modifying the polysaccharide (e.g., cellulose fibres and / or cellulosic fabric)

[0196] There is provided herein a compound of formula (XXI) for use in modifying a polysaccharide (for example, cellulose fibres and / or cellulosic fabric): wherein and y are as defined herein.

[0197] There is also provided herein a compound of formula (XXIa), for use in modifying a polysaccharide (for example, cellulose fibres and / or cellulosic fabric): wherein Y, X, A, M, Ra, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Ri, o, p, q, r, s, and t are as defined herein. In some examples, X and Y are identical.

[0198] There is provided herein a compound of formula (II) for use in modifying cellulose fibres and / or cellulosic fabric: wherein X, A, M, Ra, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Ri, o, p, q, r, s and t are as defined herein. Uses of the modified polysaccharide (e.g., the modified cellulose fibres and / or cellulosic fabric)

[0199] The modified polysaccharide described herein may be water resistant, meaning that it demonstrates improved water-resistant properties. The modified cellulose fibres and / or modified cellulosic fabric described herein may be water resistant, meaning that it demonstrates improved water-resistant properties.

[0200] There is provided herein use of polysaccharide (e.g., cellulose fibres and / or cellulosic fabric) modified with one or more compound(s) of formula (XXI) (e.g., formula (II)) as described herein for improving resistance to water uptake. For example, the polysaccharide (e.g., cellulose fibres and / or cellulosic fabric) modified with one or more compound(s) of formula (XXI) (e.g., formula (II)) as described herein show improved resistance to water uptake compared to the (corresponding) unmodified polysaccharide (e.g., unmodified cellulose fibres and / or unmodified cellulosic fabric).

[0201] For example, the % water uptake for a polysaccharide of formula (XX) modified with one or more compound(s) of formula (XXI) (e.g., formula (II)) as described herein may be at least about 5%, for example at least about 10%, or at least about 15% lower than the value of the % water uptake for the corresponding unmodified polysaccharide. For example, the % water uptake for polysaccharide modified with one or more compound(s) of formula (XXI) (e.g., formula (II)) as described herein may be from about 5% to about 80%, for example from about 10% to about 70% or from about 15% to about 60% lower than the value of the % water uptake for the corresponding unmodified polysaccharide.

[0202] For example, the % water uptake for cellulose fibres and / or cellulosic fabric modified with one or more compound(s) of formula (II) as described herein may be at least about 5%, for example at least about 10%, or at least about 15% lower than the value of the % water uptake for the corresponding unmodified cellulose fibres and / or unmodified cellulosic fabric. For example, the % water uptake for cellulose fibres and / or cellulosic fabric modified with one or more compound(s) of formula (II) as described herein may be from about 5% to about 80%, for example from about 10% to about 70% or from about 15% to about 60% lower than the value of the % water uptake for the corresponding unmodified cellulose fibres and / or unmodified cellulosic fabric. Composite material

[0203] There is provided herein a composite material comprising modified polysaccharide, wherein the polysaccharide is modified with one or more compounds of formula (XXI) (e.g., formula (II)) as described herein. There is provided herein a composite material comprising modified polysaccharide, wherein the polysaccharide is modified with one or more compounds of formula (XXI) (e.g., formula (II)) as described herein. There is provided herein a composite material comprising modified cellulose fibres and / or modified cellulosic fabric, wherein the cellulose fibres and / or cellulosic fabric is modified with one or more compound(s) of formula (II) as described herein.

[0204] The term “composite material” as used herein refers to material which is product from two or more constituent materials. These constituent materials typically have notably dissimilar chemical or physical properties and are merged to create a material with properties unlike the individual elements. Within the finished structure, the individual elements remain separate and distinct (distinguishing composite materials from mixtures and solid solutions).

[0205] In some examples, the composite material comprises a matrix having modified polysaccharide embedded therein, wherein the polysaccharide is modified with one or more compound(s) of formula (XXI) (e.g., formula (II)) as described herein. In some examples, the composite material comprises a matrix having modified cellulose fibres and / or modified cellulosic fabric embedded therein, wherein the cellulose fibres and / or cellulosic fabric is modified with one or more compound(s) of formula (II) as described herein.

[0206] The modified polysaccharide (e.g., modified cellulose and / or modified cellulosic fabric) can be used as reinforcing fibres in composite materials to provide good structural strength and engineering performance. The modified polysaccharide (e.g., modified cellulose fibres and / or modified cellulosic fabric) as described herein may be for use in reinforcing a matrix of a composite material.

[0207] The matrix may, for example, be a polymer matrix. The matrix may, for example, not be a cement matrix.

[0208] The resin used for the matrix of the composite material may, for example, be a biodegradable resin, meaning that it can be disintegrated by biological means (e.g. by enzymes and / or bacteria and / or fungi). The resin may, for example, be a biosourced resin. The resin may, for example, be biocompatible.

[0209] The resin may, for example, be selected from polyamides, polyureas, polyurethanes, polyanhydrides, poly(vinyl alcohol), poly(ethylene glycol), polyester resins (e.g. unsaturated polyester resins), polypropylene resins (PP), polylactic acid (PLA), poly(ecaprolactone), poly(alkylene succinate), epoxy resins, fatty acid-based resins, starch-based resins , cellulose-based resins (e.g. carboxymethylcellulose or hydroxyethyle cellulose), poly(amino acids) (e.g. poly(amino acids) with free carboxylic groups such as poly(aspartic acid) and poly(glutamic acid) or a combination of one or more thereof.

[0210] Method of forming a composite material

[0211] Any suitable method may be used to make the composite materials described herein.

[0212] For example, the modified polysaccharide (e.g., modified cellulose fibres and / or modified cellulosic fabrics) described herein may be embedded in a polymer matrix followed by curing of the polymer matrix. For example, the unmodified polysaccharide (e.g., unmodified cellulose fibres and / or unmodified cellulosic fabric) may be embedded in a matrix and then the polysaccharide (e.g., cellulose fibres and / or cellulosic fabric) is modified (as described herein) to produce a composite material as described herein.

[0213] The method comprises shaping the composite material into the article of manufacture simultaneously with and / or subsequently to forming the composite material. The method may, for example, comprise shaping the composite material simultaneously with forming the composite material, for example shaping the composite material into the article of manufacture directly as a prepreg.

[0214] The composite materials may be made by one or more of open mold processes such as sprayup or hand layup, a closed mold processes, a resin infusion process, resin transfer molding, reaction injection molding, vacuum-assisted resin transfer molding, resin film infusion, compression molding, injection molding, filament winding, pultrusion, tube rolling, automated fibre placement, automated tape laying, 3D-printing, centrifugal casting and extrusion.

[0215] Article of manufacture There is also provided herein an article of manufacture formed at least in part of modified polysaccharide (e.g., modified cellulose fibres and / or modified cellulosic fabric), wherein the polysaccharide (e.g., cellulose fibres and / or cellulosic fabric) is modified with one or more compound(s) of formula (XXI) (e.g., formula (II)) as described herein. There is also provided herein an article of manufacture formed at least in part of modified cellulose fibres and / or modified cellulosic fabric, wherein the cellulose fibres and / or cellulosic fabric is modified with one or more compound(s) of formula (II) as described herein.

[0216] In some examples, the article of manufacture is formed at least in part of a composite comprising modified polysaccharide (e.g., modified cellulose fibres and / or modified cellulosic fabric), wherein the polysaccharide (e.g., cellulose fibres and / or cellulosic fabric) is modified with one or more compound(s) of formula (XXI) (e.g., formula (II)) as described herein. In some examples, the article of manufacture is formed at least in part of a composite comprising modified polysaccharide of formula (XX) as described herein. In some examples, the article of manufacture is formed at least in part of a composite comprising modified cellulose fibres and / or modified cellulosic fabric, wherein the cellulose fibres and / or cellulosic fabric is modified with one or more compound(s) of formula (II) as described herein. In some examples, the article of manufacture is formed at least in part of a composite comprising modified cellulose fibres and / or modified cellulosic fabric of formula (I) as described herein.

[0217] In some examples, the composite comprises a matrix having modified polysaccharide (e.g., cellulose fibres and / or modified cellulosic fabric), wherein the polysaccharide (e.g., cellulose fibres and / or cellulosic fabric) is modified with one or more compound(s) of formula (XXI) (e.g., formula (II)) as described herein.

[0218] In some examples, the composite comprises a matrix having modified cellulose fibres and / or modified cellulosic fabric, wherein the cellulose fibres and / or cellulosic fabric is modified with one or more compound(s) of formula (I) as described herein.

[0219] The modified polysaccharide (e.g., modified cellulose fibres and / or modified cellulosic fabric) described herein may, for example, be used to make various vehicle parts, for example external or internal vehicle parts. In particular, the improved water resistance and engineering performance of the modified polysaccharide (e.g., modified cellulosic materials) described herein may enable the modified polysaccharide (e.g., modified cellulosic materials) to be used for external vehicle parts. Vehicle parts include, for example, door panels, door trim panels, floor mats, seat foams.

[0220] The vehicles may, for example, be “pods”, “pedelecs”, automobiles, airplanes, motorbikes , bicycles, boats, canoes, kayaks, paddleboards, trains or the like.

[0221] The modified polysaccharide (e.g., modified cellulose fibres and / or modified cellulosic fabric) described herein may, for example, be used in building materials, for example in flooring, cladding or insulation. The modified polysaccharide (e.g., modified cellulose fibres and / or modified cellulosic fabric) described herein may be used in building materials for garden structures (e.g. outdoor storage, gazebos, logia, trellises etc.).

[0222] The modified polysaccharide (e.g., modified cellulose fibres and / or modified cellulosic fabric) described herein may, for example, be used in medical applications such as dressings or retained surgical items (e.g., instruments, tool, devices or surgical gauze unintentionally left in the body cavity at the completion of a surgery or other procedure).

[0223] The modified polysaccharide (e.g., modified cellulose fibres and / or modified cellulosic fabric) described herein may, for example, be used in furniture, for example garden furniture.

[0224] The modified polysaccharide (e.g., modified cellulose fibres and / or modified cellulosic fabric) described herein may, for example, be used in clothing (such as jackets, coats, trousers, or footwear) or apparel (such as backpacks, rucksacks, duffel bags or chest bags).

[0225] The modified polysaccharide (e.g., modified cellulose fibres and / or modified cellulosic fabric) described herein may, for example, be used in seat upholstery (e.g., in faux leather for seats).

[0226] The article of manufacture may be formed by any suitable method. For example, a method of forming an article of manufacture may include forming the modified polysaccharide (e.g., modified cellulosic material) described herein by any of the methods described above and simultaneously with and / or subsequently to the said forming, shaping the modified polysaccharide (e.g., modified cellulosic material) into the article of manufacture. In examples, the article of manufacture may be paper, for example, a modified paper. In some embodiments, the article of manufacture may be a structural honeycomb component, a drinking cup, a food container or the like.

[0227] Embodiments of the invention

[0228] The following numbered paragraphs define particular embodiments of the present invention:

[0229] 1 . Cellulose fibres and / or cellulosic fabric of formula (I): wherein:

[0230] A is the cellulose fibres and / or cellulose fabric;

[0231] X is hydrogen, halogen, hydroxy, A or M;

[0232] M is ORa; wherein Rais C6-C30 alkyl, C6-C30 alkenyl, C6-C30 alkylcarbonyl, C6-C30 alkenylcarbonyl, CH2CH(ORc)(CH2ORd), or CH(Re)(Rf); wherein each of Rcand Rd are independently selected from hydrogen, , Ce- C30 alkyl, C6-C30 alkenyl, C6-C30 alkylcarbonyl, or C6-C30 alkenylcarbonyl; wherein Reis C1-C10 alkyl; wherein Rfis (CH2)o(CH=CH)p(CH2)qC(O)O(Ri) wherein each of Rgand Rh are independently hydrogen, halogen, hydroxy, A or M; wherein Rj is hydrogen o is 1 to 8; p is 0 or 1 ; q is 1 to 8 wherein each of Rj and Rk are independently hydrogen, Ce-Cso alkyl, Ce-Cso alkenyl, Ce- C30 alkyl carbonyl, or C6-C30 alkenylcarbonyl.

[0233] 2. The cellulose fibres and / or cellulosic fabric according to paragraph 1 , wherein A is cellulose fibres.

[0234] 3. The cellulose fibres and / or cellulosic fabric according to paragraph 1 , wherein A is cellulosic fabric.

[0235] 4. The cellulose fibres and / or cellulosic fabric according to paragraph 1 , wherein A is cellulose fibres and cellulosic fabric.

[0236] 5. The cellulose fibres and / or cellulosic fabric according to any one of paragraphs 1 to 4, wherein X is hydrogen, chloride, hydroxy, A or M.

[0237] 6. The cellulose fibres and / or cellulosic fabric according to paragraph 5, wherein X is chloride, hydroxy or M, optionally chloride.

[0238] 7. The cellulose fibres and / or cellulosic fabric according to any one of paragraphs 1 to 6, wherein M is ORaand Rais C6-C30 alkyl (for example C8-C26 alkyl, C10-C24 alkyl or C12-C22 alkyl), wherein the C6-C30 alkyl (for example C8-C26 alkyl, C10-C24 alkyl or C12-C22 alkyl) is optionally substituted with one or more of alkynyl, cycloalkyl, heterocyclyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heteroaryl, alkoxy, epoxy, haloalkoxy, carbonyl, carboxy, carboxamido, cyano, isocyano, halogen, hydroxy, amino, amido, azide, nitro, nitrate, nitrite, nitrone, diazo, diazonium, imine, phosphate, phosphite, phosphonate, phosphinate, thiol, alkylthio, arylthiol, sulfonate, sulfone, sulfoxide, disulfide, thioether or thioester.

[0239] 8. The cellulose fibres and / or cellulosic fabric according to paragraph 7, wherein Rais C12-C22 alkyl selected from dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl, nonadecyl, arachidyl, heneicosyl, behenyl, 9,10-epoxypalmityl and 9,10-epoxyoctadecyl.

[0240] 9. The cellulose fibres and / or cellulosic fabrics according to any one of paragraphs 1 to 6, wherein M is ORaand Rais C6-C30 alkenyl (for example C8-C26 alkenyl, C10- C24 alkenyl or C12-C22 alkenyl), wherein the C6-C30 alkenyl (for example C8-C26 alkenyl, C10-C24 alkenyl or C12-C22 alkenyl) is optionally substituted with one or more of alkynyl, cycloalkyl, heterocyclyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heteroaryl, alkoxy, epoxy, haloalkoxy, carbonyl, carboxy, carboxamido, cyano, isocyano, halogen, hydroxy, amino, amido, azide, nitro, nitrate, nitrite, nitrone, diazo, diazonium, imine, phosphate, phosphite, phosphonate, phosphinate, thiol, alkylthio, arylthiol, sulfonate, sulfone, sulfoxide, disulfide, thioether or thioester.

[0241] 10. The cellulose fibres and / or cellulosic fabric according to paragraph 9, wherein Rais C12-C22 alkenyl may be selected from palmitoleyl, olelyl and erucyl.

[0242] 11. The cellulose fibres and / or cellulosic fabric according to any one of paragraphs 1 to 6, wherein M is ORaand Rais C6-C30 alkylcarbonyl (for example C8-C26 alkylcarbonyl, C10-C24 alkylcarbonyl or C12-C22 alkylcarbonyl) or C6-C30 alkenylcarbonyl (for example C8-C26 alkenylcarbonyl, C10-C24 alkenylcarbonyl or C12-C22 alkenylcarbonyl).

[0243] 12. The cellulose fibres and / or cellulosic fabric according to paragraph 11 , wherein Rais a C12-C22 alkylcarbonyl or Ci2-C22 alkenylcarbonyl selected from dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, icosanoyl, docosanoyl, (9Z)-tetradec- 9-enoyl, (9Z)-hexdec-9-enoyl, (6Z)-hexadec-6-enoyl, (9Z)-octadec-9-enoyl, (E)- octadec-9-enoyl, (11E)-octadec- 11 -enoyl, (9Z,12Z)-octadec-9,12-dienoyl,

[0244] (9E, 12E)-octadeca-9, 12-dienoyl, (9Z, 12Z, 15Z)-octadeca-9, 12,15-tri enoy I , (5Z,8Z, 11 Z, 14Z)-icosa-5,8, 11 ,14-tetraenoyl, (5Z,8Z, 11 Z, 14Z, 17Z)-icosa- 5,8,11,14,17-pentanoyl, (13Z)-docos-13-enoyl and (4Z,7Z,10Z,13Z,16Z,19Z)- docosa-4,7, 10,13,16,19-hexaenoyl.

[0245] 13. The cellulose fibres and / or cellulosic fabric according to any one of paragraphs 1 to 6, wherein M is ORaand Rais CH2CH(ORc)(CH2ORd).

[0246] 14. The cellulose fibres and / or cellulosic fabric according to paragraph 13, wherein Rc alkylcarbonyl (for example C8-C26 alkylcarbonyl, C10- C24 alkylcarbonyl or C12-C22 alkylcarbonyl), C6-C30 alkenylcarbonyl (for example C8-C26 alkenylcarbonyl, C10-C24 alkenylcarbonyl or C12-C22 alkenylcarbonyl), and each of Rgand Rh are independently hydrogen, chloride, hydroxy, A or M. 15. The cellulose fibres and / or cellulosic fabric according to paragraph 14, wherein Rd is C12-C22 alkylcarbonyl or C12-C22 alkenyl carbonyl, and Rgand Rh are both chlorine.

[0247] 16. The cellulose fibres and / or cellulosic fabric according to paragraphs 14 or 15, wherein the C12-C22 alkylcarbonyl or C12-C22 alkenylcarbonyl is selected from dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, icosanoyl, docosanoyl, (9Z)-tetradec-9-enoyl, (9Z)-hexdec-9-enoyl, (6Z)-hexadec-6-enoyl, (9Z)-octadec- 9-enoyl, (E)-octadec-9-enoyl, (11E)-octadec-11-enoyl, (9Z,12Z)-octadec-9,12- dienoyl, (9E, 12E)-octadeca-9, 12-dienoyl, (9Z, 12Z, 15Z)-octadeca-9, 12, 15-trienoy I , (5Z,8Z, 11 Z, 14Z)-icosa-5,8, 11 ,14-tetraenoyl, (5Z,8Z, 11 Z, 14Z, 17Z)-icosa-

[0248] 5,8,11,14,17-pentanoyl, (13Z)-docos-13-enoyl and (4Z,7Z,10Z,13Z,16Z,19Z)- docosa-4,7, 10,13,16,19-hexaenoyl.

[0249] 17. The cellulose fibres and / or cellulosic fabric according to paragraph 11 , wherein Rcis C6-C30 alkylcarbonyl (for example C8-C26 alkylcarbonyl, C10-C24 alkylcarbonyl or C12-C22 alkylcarbonyl) or C6-C30 alkenylcarbonyl (for example C8-C26 alkenylcarbonyl, C10-C24 alkenylcarbonyl or C12-C22 alkenylcarbonyl), Rd is each of Rgand Rh are independently hydrogen, chloride, hydroxy, A or M.

[0250] 18. The cellulose fibres and / or cellulosic fabric according to paragraph 17, wherein Rcis C12-C22 alkylcarbonyl or C12-C22 alkenyl carbonyl, Rgand Rh are both chlorine.

[0251] 19. The cellulose fibres and / or cellulosic fabric according to paragraph 18, wherein the C12-C22 alkylcarbonyl or C12-C22 alkenylcarbonyl is selected from dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, icosanoyl, docosanoyl, (9Z)-tetradec- 9-enoyl, (9Z)-hexdec-9-enoyl, (6Z)-hexadec-6-enoyl, (9Z)-octadec-9-enoyl, (E)- octadec-9-enoyl, (11E)-octadec- 11 -enoyl, (9Z,12Z)-octadec-9,12-dienoyl,

[0252] (9E, 12E)-octadeca-9, 12-dienoyl, (9Z, 12Z, 15Z)-octadeca-9, 12,15-tri enoy I , (5Z,8Z, 11 Z, 14Z)-icosa-5,8, 11 ,14-tetraenoyl, (5Z,8Z, 11 Z, 14Z, 17Z)-icosa- 5,8,11,14,17-pentanoyl, (13Z)-docos-13-enoyl and (4Z,7Z,10Z,13Z,16Z,19Z)- docosa-4,7, 10,13,16,19-hexaenoyl. 20. The cellulose fibres and / or cellulosic fabric according to paragraph 11 , wherein each of Rcand Rd are independently Ce-Cso alkylcarbonyl or Ce-Cso alkenylcarbonyl.

[0253] 21. The cellulose fibres and / or cellulosic fabric according to paragraph 20, wherein each of Rcand Rd are independently C12-C22 alkylcarbonyl or C12-C22 alkenylcarbonyl selected from dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, icosanoyl, docosanoyl, (9Z)-tetradec-9-enoyl, (9Z)-hexdec-9-enoyl, (6Z)-hexadec-6-enoyl, (9Z)-octadec-9-enoyl, (E)-octadec-9-enoyl, (11E)-octadec- 11 -enoyl , (9Z, 12Z)-octadec-9, 12-dienoyl , (9E, 12E)-octadeca-9, 12-dienoyl ,

[0254] (9Z, 12Z, 15Z)-octadeca-9, 12,15-trienoy I , (5Z,8Z, 11 Z, 14Z)-icosa-5,8, 11 ,14- tetraenoyl, (5Z,8Z,11Z,14Z,17Z)-icosa-5,8,11 ,14,17-pentanoyl, (13Z)-docos-13- enoyl and (4Z,7Z, 10Z, 13Z, 16Z, 19Z)-docosa-4,7, 10,13, 16,19-hexaenoyl.

[0255] 22. The cellulose fibres and / or cellulosic fabric according to paragraphs 1 to 6, wherein M is ORaand Rais CH(Re)(Rf).

[0256] 23. The cellulose fibres and / or cellulosic fabric according to paragraph 22, wherein Reis C3-C6 alkyl and Rf is (CH2)o(CH=CH)p(CH2)qC(O)O(Rj), wherein Rj is hydrogen, and wherein o is 1 to 4, p is 0 or 1 and q is 3 to 8.

[0257] 24. The cellulose fibres and / or cellulosic fabric according to paragraph 23, wherein Reis C5 alkyl and Rf is (CH2)o(CH=CH)p(CH2)qC(O)O(Rj), wherein Rj is hydrogen, wherein o is 1 , p is 1 and q is 8.

[0258] 25. The cellulose fibres and / or cellulosic fabric according to paragraph 22, wherein Reis C3-C6 alkyl and Rf is (CH2)o(CH=CH)p(CH2)qC(O)O(Rj), wherein Rj is , wherein o is 1 to 4, p is 0 or 1 and q is 3 to 8, and wherein each of Rj and Rk are independently C6-C30 alkyl, C6-C30 alkenyl, C6-C30 alkyl carbonyl, or Ce- C30 alkenylcarbonyl.

[0259] 26. The cellulose fibres and / or cellulosic fabric according to paragraph 25, wherein each of Rj and Rk is C12-C22 alkylcarbonyl, or C12-C22 alkenylcarbonyl, and wherein the C12-C22 alkylcarbonyl, or C12-C22 alkenylcarbonyl is optionally substituted with one or more of alkynyl, cycloalkyl, heterocyclyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heteroaryl, alkoxy, epoxy, haloalkoxy, carbonyl, carboxy, carboxamido, cyano, isocyano, halogen, hydroxy, amino, amido, azide, nitro, nitrate, nitrite, nitrone, diazo, diazonium, imine, phosphate, phosphite, phosphonate, phosphinate, thiol, alkylthio, arylthiol, sulfonate, sulfone, sulfoxide, disulfide, thioether or thioester. The cellulose fibres and / cellulosic fabric according to paragraphs 25 or 26, wherein Reis Cs alkyl and Rf is (CH2)o(CH=CH)p(CH2)qC(O)O(Rj), wherein Rj is

[0260] ORj k

[0261] , wherein o is 1 , p is 1 and q is 8, wherein each of Rj and Rk are independently C12-C22 alkylcarbonyl, or Ci2-C22 alkenylcarbonyl. The cellulose fibres and / or cellulosic fabric according to paragraphs 26 or 29, wherein each of Rj and Rk are independently a C12-C22 alkylcarbonyl or C12-C22 alkenylcarbonyl selected from dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, icosanoyl, docosanoyl, (9Z)-tetradec-9-enoyl, (9Z)-hexdec-9-enoyl, (6Z)-hexadec-6-enoyl, (9Z)-octadec-9-enoyl, (E)-octadec-9-enoyl, (11E)-octadec- 11 -enoyl , (9Z, 12Z)-octadec-9, 12-dienoyl , (9E, 12E)-octadeca-9, 12-dienoyl ,

[0262] (9Z, 12Z, 15Z)-octadeca-9, 12,15-trienoy I , (5Z,8Z, 11 Z, 14Z)-icosa-5,8, 11 ,14- tetraenoyl, (5Z,8Z,11Z,14Z,17Z)-icosa-5,8,11 ,14,17-pentanoyl, (13Z)-docos-13- enoyl and (4Z,7Z, 10Z, 13Z, 16Z, 19Z)-docosa-4,7, 10,13, 16,19-hexaenoyl. The cellulose fibres and / or cellulosic fabric according to paragraph 22, wherein Re

[0263] ORj ^ “°Rkis C5 alkyl and Rf is (CH2)o(CH=CH)p(CH2)qC(O)O(Rj), wherein Rj is < wherein o is 1 , p is 1 and q is 8, wherein each of Rj and Rk are - C(O)(CH2)r(CH=CH)sCH2CH(ORi)(CH2)tCH3, wherein r is 1 to 8, s is 0 or 1 and t is

[0264] 1 to 4, and wherein each of Rgand Rh are independently selected hydrogen, chloride, hydroxy, A or M. The cellulose fibres and / or cellulosic fabric according to paragraph 29, wherein r is 8, s is 1 and t is 4, and Rgis A and Rh is chlorine. 31. The cellulose fibres and / or cellulosic fabric according to paragraph 29, wherein r is 8, s is 1 and t is 4, and both Rgand Rh are chlorine.

[0265] 32. The cellulose fibres and / or cellulosic fabric according to any one of paragraphs 1 to 4, wherein the one or more compound(s) of formula (I) is / are selected from:

[0266]

[0267] 33. The cellulose fibres and / or cellulosic fabric according to any one of paragraphs 1 to 32, wherein the modification covalently links to the cellulose fibres and / or cellulosic fabric, for example via an ether linkage. 34. A method for preparing cellulose fibres and / or cellulosic fabric according to any one of paragraphs 1 to 33, the method comprising the step of reacting cellulose fibres and / or cellulosic fabric with one or more compound(s) of formula (II): wherein X, A, M, Ra, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Ri, o, p, q, r, s and t are as defined in any one of paragraphs 1 to 33.

[0268] 35. A composite material comprising modified cellulose fibres and / or modified cellulosic fabric, wherein the cellulose fibres and / cellulosic fabric is of formula (I) according to any one of paragraphs 1 to 33, or the modified cellulose fibres and / or cellulosic fabric is prepared according to the method of paragraph 34.

[0269] 36. The composite material according to paragraph 35, wherein the modified cellulose fibres and / or cellulosic fabric is embedded in a matrix.

[0270] 37. An article of manufacture formed at least in part of a composite material according to paragraphs 35 or 36.

[0271] 38. An article of manufacture formed at least in part of modified cellulose fibres and / or modified cellulosic fabric, wherein the cellulose fibres and / cellulosic fabric is of formula (I) according to any one of paragraphs 1 to 33, or the modified cellulose fibres and / or cellulosic fabric is prepared according to the method of paragraph 34.

[0272] 39. Use of cellulose fibres and / or cellulosic fabric according to any one of paragraphs 1 to 33 for improving resistance to water uptake (for example improving resistance to water uptake compared to the unmodified cellulose fibres and / or cellulosic fabric).

[0273] EXAMPLES

[0274] Example 1 - Methods of modifying cellulosic fabric

[0275] Measurement methods

[0276] Scanning electron microscope (SEM) images were obtained using a Gemini SEM 300 SEM (Zeiss, Oberkochen, Germany). All samples were attached to SEM stubs using double-sided adhesive tape and then coated with gold using a Polaron SC7640 sputter gold coater (Quorum Technologies, Lauphton, UK) prior to imaging, operating at an accelerating voltage of 5 kV. Widths of the fibres were analysed by the Imaged software.

[0277] X-ray powder diffraction (XRD) was measured using a Rigaku Smartlab SE® powder diffractometer (Rigaku Europe SE, Neu-lsenburg, Germany). Diffraction scattering patterns were collected at room temperature using monochromatic Cu Ka radiation (A = 1.5418 A) with 20 in the range from 10° to 60° with a step width of 0.02° and a scan speed of 4° min-1.

[0278] Synthesis derivatised cyanuric chloride

[0279] A round bottom flask was charged with cyanuric chloride (339 mg, 1.85 mmol, 1 equiv.), octadecanol (500 mg, 1.85 mmol, 1 equiv.) and sodium bicarbonate (309 mg, 3.7 mmol, 2 equiv.) and heated to 65 °C for 150 minutes. The reaction mixture was allowed to cool, dissolved in dichloromethane, filtered to remove solids, and solvent removed to obtain 2,4-dichloro-6-octadecyloxy-1,3,5-triazine as a white solid.

[0280] Modified cellulosic fabric - Aqueous treatment method (method 1)

[0281] Sodium carbonate (8 g) was dissolved in distilled water (750 mL) and warmed to 40 °C. 2,4-dichloro-6-octadecyloxy-1,3,5-triazine (6 g) was suspended in distilled water (80 mL), and A / -lauryl sarcosine sodium salt (2 g) was added. The suspension was stirred vigorously until an emulsion was formed. The resulting emulsion was then poured into the sodium carbonate solution. The example fabric (500gsm woven hemp, or 300gsm woven flax, or 450gsm nonwoven flax felt) was submerged for 3 hours with stirring. The fabric was removed and allowed to dry over 48 hours. The example fabric was then cured in the oven for 1 hour at 120 °C.

[0282] Modified cellulose fabric - Organic treatment method (method 2) 2,4-dichloro-6-octadecyloxy-1,3,5-triazine (5 g) was added to acetone (250 mL) to prepare a saturated solution. The example fabric (500gsm woven hemp, or 300gsm woven flax, or 450gsm nonwoven flax felt) was then submerged in this solution for 40 minutes, removed, and cured in an oven at 120 °C for 10 minutes. The example fabric was then washed in excess acetone and allowed to dry.

[0283] Table 1 shows the % crystallinity, crystallite size and interplanar distance values (obtained from XRD plots) for untreated hemp fabric and hemp fabric treated as described in method 2.

[0284] Table 1

[0285] Figure 2 shows (A) a SEM image of a representative cellulose fibre, for hemp fabric treated as described in method 2; and (B) the distribution of fibre widths (as measured by XRD), for hemp fabric treated as described in method 2.

[0286] Table 2 shows the % crystallinity, crystallite size and interplanar distance values (obtained from XRD) plots for untreated flax fabric and flax fabric treated as described in method 2.

[0287] Table 2

[0288] Figure 3 shows (A) an SEM image of a representative cellulose fibre, for flax fabric treated as described in method 2; and (B) the distribution of fibre widths (as measured XRD), for flax fabric treated as described in method 2.

[0289] Example 2 - Moisture absorption of modified cellulose fabrics

[0290] The cellulosic material samples prepared according to the organic treatment method of

[0291] Example 1 were cut into three squares of approximately 0.25 g weight. Each sample was immersed in deionised water. The samples were removed from the water after 72 hours or 144 hours or 168 hours, surface liquid was removed from the samples and the samples were immediately weighed. The process was repeated periodically (e.g., every 24 hours) until the fabric reached saturation.

[0292] This process was repeated for the untreated flax, felt and hemp fabrics.

[0293] The weight gain curves were plotted for % weight change (Wuptake), or normalised weight gain (Wtn), versus total cumulative soaking time. The difference in weight between the sample in dry condition and after water immersion at time t was calculated as follows:

[0294] Wuptake (%) = [(Wt - Wo) / Wo] X 100

[0295] Where Wuptake = water uptake, Wt= weight of the sample at immersion time t corrected to correspond to 1 g of dry fabric, and Wo = initial weight of the sample corrected to correspond to 1 g of dry fabric.

[0296] The results of the water uptake test for untreated and treated flax, felt and hemp fabrics at specified immersion times are provided in Tables 1 to 3 and Figures 4 to 6.

[0297] Table 3 and Figure 4 show the % water uptake values after immersion in water durations shown below, for three untreated hemp fabrics (A, B and C) and a hemp fabric treated according to the method of Example 1 (D).

[0298] Table 3 Table 4 and Figure 5 show the % water uptake values after immersion in water for durations shown below, for three untreated flax fabrics (A, B and C) and a flax fabric treated according to the method of Example 1 (D).

[0299] Table 4

[0300] Table 5 and Figure 6 show the % water uptake values after immersion in water for durations shown below, for three untreated felt fabrics (A, B and C) and a felt fabric treated according to the method of Example 1 (D).

[0301] Table 5

[0302] The results of the water uptake test in Tables 3 to 5 as well as in Figures 4 to 6 show that modified cellulose materials according to the present invention have reduced % weight gain after immersion in water compared to untreated cellulose materials. Thus, the modified cellulose materials according to the present invention have improved resistances to water uptake versus untreated cellulose materials. The forgoing broadly describes certain embodiments of the present invention without limitation. Variations and modifications as will be readily apparent to those skilled in the art are intended to be within the scope of the present invention as defined in and by the appended claims.

[0303] Further embodiments

[0304] The following numbered paragraphs define embodiments of the invention.

[0305] 1 . Cellulose fibres and / or cellulosic fabric of formula (I): wherein:

[0306] A is the cellulose fibres and / or cellulose fabric;

[0307] X is hydrogen, halogen, hydroxy, A or M;

[0308] M is ORa; wherein Rais C6-C30 alkyl, C6-C30 alkenyl, C6-C30 alkylcarbonyl, C6-C30 alkenylcarbonyl, CH2CH(ORc)(CH2ORd), or CH(Re)(Rf); wherein each of Rcand Rd are independently selected from hydrogen, , C6-

[0309] C30 alkyl, C6-C30 alkenyl, C6-C30 alkylcarbonyl, C6-C30 alkenylcarbonyl, or P(O)(OCi- Csalkyl)2; wherein Reis C1-C10 alkyl; wherein Rfis (CH2)o(CH=CH)p(CH2)qC(O)O(Ri) wherein each of Rgand Rh are independently hydrogen, halogen, hydroxy, A or M; wherein Rj is hydrogen o is 1 to 8; p is 0 or 1; q is 1 to 8 wherein each of Rj and Rk are independently hydrogen, C6-C30 alkyl, C6-C30 alkenyl, Ce- C30 alkyl carbonyl, or C6-C30 alkenylcarbonyl.

[0310] 2. The cellulose fibres and / or cellulosic fabric according to paragraph 1 , wherein X is chlorine.

[0311] 3. The cellulose fibres and / or cellulosic fabric according to paragraphs 1 or 2, wherein M is ORaand Rais C6-C30 alkyl.

[0312] 4. The cellulose fibres and / or cellulosic fabric according to paragraph 3, wherein the C6-C30 alkyl is selected from dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl, nonadecyl, arachidyl, heneicosyl, behenyl, 9,10-epoxypalmityl and 9,10- epoxyoctadecyl.

[0313] 5. The cellulose fibres and / or cellulosic fabric according to paragraphs 1 or 2, wherein M is ORaand Rais C6-C30 alkenyl.

[0314] 6. The cellulose fibres and / or cellulosic fabric according to paragraphs 5, wherein the C6-C30 alkenyl is selected palmitoleyl, olelyl and erucyl.

[0315] 7. The cellulose fibres and / or cellulosic fabric according to paragraphs 1 or 2, wherein M is ORaand Rais C6-C30 alkylcarbonyl (for example C8-C26 alkylcarbonyl, C10- C24 alkylcarbonyl or C12-C22 alkylcarbonyl) or C6-C30 alkenylcarbonyl (for example Cs- C26 alkenylcarbonyl, C10-C24 alkenylcarbonyl or C12-C22 alkenylcarbonyl).

[0316] 8. The cellulose fibres and / or cellulosic fabric according to paragraph 7, wherein Rais a C12-C22 alkylcarbonyl or C12-C22 alkenylcarbonyl selected from dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, icosanoyl, docosanoyl, (9Z)-tetradec-9- enoyl, (9Z)-hexdec-9-enoyl, (6Z)-hexadec-6-enoyl, (9Z)-octadec-9-enoyl, (E)-octadec- 9-enoyl, (11E)-octadec-11-enoyl, (9Z,12Z)-octadec-9,12-dienoyl, (9E,12E)-octadeca- 9, 12-dienoyl, (9Z, 12Z, 15Z)-octadeca-9, 12,15-tri enoy I , (5Z,8Z, 11 Z, 14Z)-icosa- 5,8,11 ,14-tetraenoyl, (5Z,8Z, 11 Z, 14Z, 17Z)-icosa-5,8, 11 ,14,17-pentanoyl , (13Z)-docos- 13-enoyl and (4Z,7Z, 10Z, 13Z, 16Z, 19Z)-docosa-4,7, 10, 13,16,19-hexaenoyl.

[0317] 9. The cellulose fibres and / or cellulosic fabric according to paragraphs 1 or 2, wherein M is ORaand Rais CH2CH(ORc)(CH2ORd).

[0318] 10. The cellulose fibres and / or cellulosic fabric according to paragraph 9, wherein Rc alkylcarbonyl or C6-C30 alkenylcarbonyl.

[0319] 11 . The cellulose fibres and / or cellulosic fabric according to paragraph 10, wherein

[0320] Rgand Rh are both chlorine, and Rd is C12-C22 alkyl carbonyl or C12-C22 alkenylcarbonyl. 12. The cellulose fibres and / or cellulosic fabric according to paragraph 9, wherein Rcis C6-C30 alkylcarbonyl or Ce-Cso alkenylcarbonyl,

[0321] 13. The cellulose fibres and / or cellulosic fabric according to paragraph 12, wherein Rcis C12-C22 alkyl carbonyl or C12-C22 alkenylcarbonyl, and Rgand Rh are both chlorine.

[0322] 14. The cellulose fibres and / or cellulosic fabric according to paragraphs 1 or 2, wherein M is ORa, and Rais CH(Re)(Rf).

[0323] 15. The cellulose fibres and / or cellulosic fabric according to paragraph 14, wherein Reis Cs alkyl and Rf is (CH2)o(CH=CH)p(CH2)qC(O)O(Rj), wherein o is 1 , p is 1 and q is 8.

[0324] 16. The cellulose fibres and / or cellulosic fabric according to paragraphs 14 or 15, wherein Rj is H.

[0325] 17. The cellulose fibres and / or cellulosic fabric according to paragraphs 14 or 15, ORj

[0326] J- °Rkwherein Rj is , and wherein each of Rj and Rk are independently C6-C30 alkylcarbonyl, or C6-C30 alkenylcarbonyl.

[0327] 18. The cellulose fibres and / or cellulosic fabric according to paragraph 14, wherein

[0328] Reis C5 alkyl and Rf is (CH2)o(CH=CH)p(CH2)gC(O)O(Rj), wherein wherein o is 1 , p is 1 and q is 8, wherein each of Rj and Rk are -

[0329] C(O)(CH2)r(CH=CH)sCH2CH(ORi)(CH2)tCH3, wherein r is 1 to 8, s is 0 or 1 and t is 1 to

[0330] 4, and wherein each of Rgand Rh are independently selected hydrogen, chloride, hydroxy, A or M.

[0331] 19. The cellulose fibres and / or cellulosic fabric according to paragraph 18, wherein r is 8, s is 1 and t is 4, and Rgis A and Rh is chlorine; or wherein r is 8, s is 1 and t is 4, and both Rgand Rh are chlorine.

[0332] 20. The cellulose fibres and / or cellulosic fabric according to paragraph 1 , wherein the one or more compound(s) of formula (I) is / are selected from:

[0333] šnd

[0334] 21 . The cellulose fibres and / or cellulosic fabric according to any one of paragraphs 1 to 20, wherein the modification covalently links to the cellulose fibres and / or cellulosic fabric, for example via an ether linkage.

[0335] 22. Use of cellulose fibres and / or cellulosic fabric according to any one of paragraphs 1 to 21 for improving resistance to water uptake.

[0336] 23. A method for preparing cellulose fibres and / or cellulosic fabric according to any one of paragraphs 1 to 21 , the method comprising the step of reacting cellulose fibres and / or cellulosic fabric with one or more compound(s) of formula (II): wherein X, A, M, Ra, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Ri, o, p, q, r, s and t are as defined in any one of paragraphs 1 to 21.

[0337] 24. An article of manufacture formed at least in part of modified cellulose fibres and / or modified cellulosic fabric, wherein the cellulose fibres and / cellulosic fabric is of formula (I) according to any one of paragraphs 1 to 21 , or wherein the modified cellulose fibres and / or cellulosic fabric is prepared according to the method of paragraph 23. 25. A composite material comprising modified cellulose fibres and / or modified cellulosic fabric, wherein the cellulose fibres and / or cellulosic fabric is of formula (I) according to any one of paragraphs 1 to 21, or wherein the modified cellulose fibres and / or the modified cellulosic fabric is prepared according to the method of paragraph 23.

[0338] 26. The composite material according to paragraph 25, wherein the modified cellulose fibres and / or modified cellulosic fabric is embedded in a matrix. 27. An article of manufacture formed at least in part of a composite material according to paragraphs 25 or 26.

Claims

1. CLAIMS1 . A polysaccharide of formula (XX):wherein:Ring Z is a 5- or 6-membered heteroaromatic ring containing from 1 to 4 nitrogen atoms;A is the polysaccharide;X is hydrogen, halogen, hydroxy, A, M, or an electron-withdrawing functional group;M is ORa; a is 1 ; m is 1 ; x is 0 to 3, wherein a+m+x does not exceed the total number of substituents possible on heteroaromatic ring Z; wherein Rais Ce-Cso alkyl, Ce-Cso alkenyl, Ce-Cso alkylcarbonyl, Ce-Cso alkenylcarbonyl, CH2CH(ORc)(CH2ORd), or CH(Re)(Rf); wherein each of Rcand Rd are independently selected from hydrogen, Z", Ce-Cso alkyl, Ce-Cso alkenyl, C6-C30 alkylcarbonyl, C6-C30 alkenylcarbonyl, or P(O)(OCi-C3alkyl)2; wherein Reis C1-C10 alkyl; wherein Rfis (CH2)o(CH=CH)p(CH2)qC(O)O(Ri) whereinRing Z' is a 5- or 6-membered heteroaromatic ring containing 1 to 4 nitrogen atoms; wherein each of Rgand Rh are independently hydrogen, halogen, hydroxy, A or M; wherein g and h are independently from 1 to 4 and g+h does not exceed the total number of substituents possible on heteroaromatic ring Z';wherein Rj is hydrogeno is 1 to 8; p is 0 or 1 ; q is 1 to 8 wherein each of Rj and Rk are independently hydrogen, Ce-Cso alkyl, Ce-Cso alkenyl, Ce- C30 alkyl carbonyl, or C6-C30 alkenylcarbonyl.

2. The polysaccharide according to claim 1 , wherein A is selected from cellulose fibres and / or cellulose fabric.

3. The polysaccharide according to claims 1 or 2, wherein formula (XX) is a compound of formula (I)wherein X is hydrogen, halogen, hydroxy, A, or M.

4. The polysaccharide according to claims 1 to 3, wherein X is halogen, for example, chlorine.

5. The polysaccharide according to claims 1 to 4, wherein M is ORaand Rais C6-C30 alkyl.

6. The polysaccharide according to claim 5, wherein the C6-C30 alkyl is selected from dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl, nonadecyl, arachidyl, heneicosyl, behenyl, 9,10-epoxypalmityl and 9,10-epoxyoctadecyl.

7. The polysaccharide according to claims 1 to 4, wherein M is ORaand Rais C6-C30 alkenyl.

8. The polysaccharide according to claims 7, wherein the C6-C30 alkenyl is selected palmitoleyl, olelyl and erucyl.

9. The polysaccharide according to claims 1 to 4, wherein M is ORaand Rais C6-C30 alkylcarbonyl (for example C8-C26 alkylcarbonyl, C10-C24 alkylcarbonyl or C12-C22 alkylcarbonyl) or C6-C30 alkenylcarbonyl (for example C8-C26 alkenylcarbonyl, C10-C24 alkenylcarbonyl or C12-C22 alkenylcarbonyl).

10. The polysacharide according to claim 9, wherein Rais a C12-C22 alkylcarbonyl or C12-C22 alkenylcarbonyl selected from dodecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, icosanoyl, docosanoyl, (9Z)-tetradec-9-enoyl, (9Z)-hexdec-9-enoyl, (6Z)- hexadec-6-enoyl, (9Z)-octadec-9-enoyl, (E)-octadec-9-enoyl, (11E)-octadec-11-enoyl,(9Z, 12Z)-octadec-9, 12-dienoyl, (9E, 12E)-octadeca-9, 12-dienoyl, (9Z, 12Z, 15Z)- octadeca-9, 12, 15-tri enoyl , (5Z,8Z, 11 Z, 14Z)-icosa-5,8, 11,14-tetraenoyl,(5Z,8Z, 11Z, 14Z, 17Z)-icosa-5,8, 11 , 14, 17-pentanoyl, (13Z)-docos-13-enoyl and(4Z,7Z, 10Z, 13Z, 16Z, 19Z)-docosa-4,7, 10,13,16,19-hexaenoyl.

11. The polysaccharide according to claims 1 to 4, wherein M is ORaand RaisCH2CH(ORc)(CH2ORd).

12. The polysaccharide according to claim 11, wherein Rcis Z', and Rd is Ce-Cso alkylcarbonyl or Ce-Cso alkenylcarbonyl; optionally wherein13. The polysaccharide according to claim 12, wherein Rgand Rh are both chlorine, and Rd is Ci2-C22alkyl carbonyl or Ci2-C22alkenylcarbonyl.

14. The cellulose fibres and / or cellulosic fabric according to claim 9, wherein Rcis Ce- C30 alkylcarbonyl or C6-C30 alkenylcarbonyl, and Rd is Z', optionally wherein Z' is15. The polysaccharide according to claim 14, wherein Rcis Ci2-C22alkyl carbonyl or Ci2-C22alkenylcarbonyl, and Rgand Rh are both chlorine.

16. The polysaccharide according to claims 1 to 4, wherein M is ORa, and Rais CH(Re)(Rf).

17. The polysaccharide according to claim 14, wherein Reis C5 alkyl and Rf is (CH2)o(CH=CH)p(CH2)qC(O)O(Rj), wherein o is 1 , p is 1 and q is 8.

18. The polysaccharide according to claims 16 or 17, wherein Rj is H.

19. The polysaccharide according to claims 16 or 17, whereinwherein each of Rj and Rk are independently C6-C30 alkylcarbonyl, or C6-C30 alkenylcarbonyl.

20. The polysaccharide according to claim 16, wherein Reis C5 alkyl and Rf is (CH2)o(CH=CH)p(CH2)qC(O)O(Rj), wherein, wherein o is 1, p is 1 and q is 8, wherein each of Rj and Rkare -C(O)(CH2)r(CH=CH)sCH2CH(ORi)(CH2)tCH3,wherein r is 1 to 8, s is 0 or 1 and t is 1 to 4, and wherein Ri is Z' and each of Rgand Rh are independently selected hydrogen, chloride, hydroxy, A or M, optionally wherein21. The polysaccharide according to claim 20, wherein r is 8, s is 1 and t is 4, and Rgis A and Rh is chlorine; or wherein r is 8, s is 1 and t is 4, and both Rgand Rh are chlorine.

22. The polysaccharide according to claim 1, wherein the one or more compound(s) of formula (I) is / are selected from:

23. The polysaccharide according to any one of claims 1 to 22, wherein the modification covalently links to the polysaccharide, for example via an ether linkage.

24. Use of a polysaccharide according to any one of claims 1 to 23 for improving resistance to water uptake.

25. A method for preparing a polysaccharide according to any one of claims 1 to 23 , the method comprising the step of reacting a polysaccharide with one or more compound(s) of formula (XXI):wherein X, A, M, Ra, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Ri, o, p, q, r, s, t, m and x are as defined in any one of claims 1 to 23; and wherein Y is a leaving group, y is at least 1 , and m+x+y does not exceed the total number of substituents possible on heteroaromatic ring Z.

26. An article of manufacture formed at least in part of modified polysaccharide, wherein the polysaccharide is of formula (XX) according to any one of claims 1 to 23, or wherein the modified polysaccharide is prepared according to the method of claim 25, optionally wherein formula (XX) is formula (I).

27. A composite material comprising modified polysaccharide wherein the polysaccharide is of formula (XX) according to any one of claims 1 to 23, or wherein the modified polysaccharide is prepared according to the method of claim 25, optionally wherein formula (XX) is formula (I).

28. The composite material according to claim 27, wherein the modified polysaccharide is embedded in a matrix, and optionally, wherein the modified polysaccharide is modified cellulose fibres and / or modified cellulosic fabric.

29. An article of manufacture formed at least in part of a composite material according to claims 27 or 28.

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