Antibiofouling compositions

Abstract

Provided is a composition comprising: a substrate; a linker attached to the substrate, said linker comprising a hydrophobic moiety; and a functional moiety comprising a semi-hydrophobic group and / or a hydrophilic group; wherein the functional moiety is coupled to the linker and comprises a hydroxyl, amino or thiol group or a derivative thereof. Also disclosed herein is process for preparing a composition comprising: combining a substrate, a linker or precursor thereto comprising a hydrophobic moiety and a functional molecule comprising a semi-hydrophobic or hydrophilic group and a hydroxyl, amino or thiol group, to form a blend, and melt processing the blend. Compositions are useful for reducing biofouling of surfaces.

Description

Antibiofouling compositionsCross-reference to related applications

[0001] The present application claims priority to Australian Provisional Patent Application No.2025901019, filed on 28 March 2025, the entire disclosure of which is incorporated herein by cross-reference.Field of the disclosure

[0002] The present disclosure broadly relates to compositions for reducing biofouling of surfaces.Background of the disclosure

[0003] Any discussion of the prior art throughout this specification should in no way be considered as an admission that such prior art is widely known or forms part of the common general knowledge in the field.

[0004] In many applications in which synthetic items come in contact with biological materials there is a need to reduce adhesion of biological materials such as proteins, nucleosides, platelets, viruses, fungi, bacteria etc. to the surface of such items. Adhesion of biological materials to a surface may be considered as biofouling. Commonly materials which have suitable bulk physical properties for these items do not have suitable surface chemistry for reducing biofouling.

[0005] Consequently, much research has been conducted into surface treatments which can be applied to a bulk item in order to reduce biofouling. However treatments that have been developed to date commonly suffer from long term degradation, particularly when exposed to stress factors such as variations in temperature, pH, salinity etc.

[0006] There is therefore a need for a robust surface treatment which can be applied to a variety of substrates in order to confer antibiofouling properties or to tailor the substrate for specific applications.Summary of the disclosure

[0007] In a first aspect there is provided a composition comprising:• a substrate;ME_962110409_1• a linker attached to the substrate, said linker comprising a hydrophobic moiety; and• a functional moiety comprising a semi-hydrophobic group and / or a hydrophilic group.

[0008] The functional moiety may be coupled to the linker. It may comprise a hydroxyl, amino or thiol group or a derivative thereof.

[0009] The following options may be used in conjunction with the first aspect, either individually or in any suitable combination.

[0010] The linker may be attached covalently to the substrate.

[0011] The substrate may be a polymer. It may be a polymer comprising an ester or amide linkage. It may be a polyester or a polyamide. It may be a silicone. It may be selected from the group consisting of a polyester, a polyamide, a silicone and a hydrocarbon polymer.

[0012] The substrate may comprise an inorganic substance. It may comprise a surface treated calcium carbonate. It may comprise a surface treated calcium carbonate which is a fatty acid coated calcium carbonate. It may comprise silica. The silica may be surface treated, e.g. hydrophobed. It may be surface treated so as to impart hydrophobic groups, e.g. alkylsilyl (in particular trialkylsilyl) groups on the surface.

[0013] The substrate may be particulate.

[0014] The composition may be dispersed within a polymeric matrix.

[0015] The linker may comprise a hydrocarbon chain, e.g. a C2 or C3 hydrocarbon chain. It may be, or may be derived from, a bis-carboxylic acid or a cyclic carbonate or a cyclic anhydride or a lactam or a bis-amide or a cyclic imide

[0016] The functional moiety may be covalently coupled to the linker. It may comprise an ether linkage. It may comprise a polyether chain. It may comprise a polyoxyethylene group. It may have a functional headgroup attached to the hydroxyl, amino or thiol group. The functional headgroup attached to said hydroxyl, amino or thiol group may be the derivative thereof.

[0017] The functional headgroup may be capable of one or more of:• improving biocompatibility and / or haemocompatibility of the composition;• enhancing affinity of the composition to water molecules;ME_962110409_1• reducing protein unfolding;• enhancing lubricity of the composition;• enhancing resistance of the composition to oxidation;• enabling site-specific recognition and / or bioconjugation and / or immobilisation of biomolecules on the composition;• enabling branching and / or crosslinking of the composition.

[0018] In an embodiment there is provided a composition comprising:• a polymeric substrate;• a linker attached to the substrate, said linker comprising a hydrophobic moiety; and• a functional moiety comprising a semi-hydrophobic group and / or a hydrophilic group;wherein the functional moiety is coupled to the linker and comprises a hydroxyl, amino or thiol group or a derivative thereof.

[0019] In another embodiment there is provided a composition comprising:• a particulate inorganic substrate;• a linker attached to the substrate, said linker comprising a hydrophobic moiety; and• a functional moiety comprising a semi-hydrophobic group and / or a hydrophilic group;wherein the functional moiety is coupled to the linker and comprises a hydroxyl, amino or thiol group or a derivative thereof.

[0020] In yet another embodiment there is provided a composition comprising:• a particulate inorganic substrate;• a linker attached to the substrate, said linker comprising a hydrophobic moiety; and• a functional moiety comprising a semi-hydrophobic group and / or a hydrophilic group;ME_962110409_1wherein the functional moiety is coupled to the linker and comprises a hydroxyl, amino or thiol group or a derivative thereof;said composition being dispersed within a polymeric matrix.

[0021] In a second aspect there is provided a process for preparing a composition comprising:• combining a substrate, a linker or precursor thereto comprising a hydrophobic moiety and a functional molecule comprising a semi-hydrophobic or hydrophilic group and a hydroxyl, amino or thiol group, to form a blend, and• melt processing the blend.

[0022] The following options may be used in conjunction with the second aspect, either individually or in any suitable combination.

[0023] The substrate may comprise a polymer. It may comprise an ester or an amide linkage.

[0024] The linker precursor may comprise a cyclic carbonate or an α,β-unsaturated carbonyl compound. It may be selected from the group consisting of an optionally substituted ethylene carbonate, an α,β-unsaturated carboxylic acid or dicarboxylic acid, an α,β-unsaturated ester or diester, an α,β-unsaturated anhydride, an α,β-unsaturated amide or diamide and an α,β-unsaturated lactam, wherein optional substituents on ethylene carbonate are selected from C1 to C6 straight chain, branched and cyclic alkanes.

[0025] The melt processing may be conducted at a temperature of between about 150 and about 250°C. In some instances the melt processing is conducted in the presence of a free radical initiator (e.g. a peroxide, peroxyacid, peroxyester, azo compound). In these instances, the melt processing may be conducted at a temperature of about, or at least about, the 10 hour half-life temperature of the initiator, or of about, or at least about, the 5, 2 or 1 hour halflife temperature thereof.

[0026] The process may comprise attaching a functional headgroup to the hydroxyl, amino or thiol group.

[0027] The process may additionally comprise combining the composition with a polymer, e.g. by melt processing.ME_962110409_1

[0028] The process of the second aspect may produce a composition according to the first aspect. The composition of the first aspect may be produced by the process of the second aspect.

[0029] There is also disclosed a composition made by the second aspect.

[0030] There is also disclosed a composition comprising a polymeric matrix having a composition according to the first aspect, or a composition made by the second aspect, dispersed therethrough.

[0031] There is also disclosed a method for surface modification of a substrate comprising exposing said substrate to: a linker, said linker comprising a hydrophobic moiety; and a functional moiety comprising a semi-hydrophobic group and / or a hydrophilic group.Definitions

[0032] The following are some definitions that may be helpful in understanding the description of the present disclosure. These are intended as general definitions and should in no way limit the scope of the present disclosure to those terms alone, but are put forth for a better understanding of the following description.

[0033] Where mention is made herein of X and Y, this may refer to a reactive monomer, or to a polymer or oligomer made from the reactive monomer, or to a block of the polymer or oligomer within a block copolymer. Which of these is intended will be apparent from the context in each case.

[0034] Where mention is made herein of X' or X", this refers to a species which is within the definition of X as defined herein but may be different from the earlier mention of X. For example, in the description of X, detailed elsewhere herein, X is defined as a semihydrophobic component, with examples being, inter alia, a polyol polyester, adipic acid and a partially hydrolysed plant glyceride. Therefore in a particular example X may be a polyol polyester, X' may be adipic acid and X" may be a partially hydrolysed plant glyceride. Similarly, where mention is made of Y' and Y", this refers to a species which is within the definition of Y as defined herein but may be different from the earlier mention of Y, and where mention is made of W and W', this refers to a species which is within the definition of W as defined herein but may be different from the earlier mention of W.ME_962110409_1

[0035] Throughout this specification, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps. The term "consist" or variations thereof will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, and the exclusion of any other element, integer or step, or group of elements, integers or steps. The term "consist essentially" or variations thereof will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, and the exclusion of any other element, integer or step, or group of elements, integers or steps other than incidental elements, integers or steps or those that have negligible effect on the operation of the invention.

[0036] The terms "a" and "an" are used herein to refer to one or to more than one (i.e. to at least one) of the grammatical object of the article. By way of example, "an element" means one element or more than one element.

[0037] In the context of this specification the term "about" is understood to refer to a range of numbers that a person of skill in the art would consider equivalent to the recited value in the context of achieving the same function or result. The term "about" may refer to ±10% of the recited value.

[0038] The term "may incorporates both positive and negative alternatives unless the context indicates otherwise. Thus for example, " A may be B" encompasses the options " A is B" and " A is not B".

[0039] Any numerical range recited herein is intended to include all sub-ranges of the same numerical precision subsumed within the recited range. For example, a range of 1.0 to 5.0 is intended to include all sub-ranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 5.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 5.0, such as 2.1 to 4.5. Any maximum numerical limitation recited herein is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited herein is intended to include all higher numerical limitations subsumed therein.

[0040] The term "hydrocarbon" refers to compounds of containing only carbon and hydrogen. They may be aliphatic or may be aromatic. Aliphatic hydrocarbons may be polymeric, commonly waxes, or may be monomeric. Monomeric hydrocarbons may be linear or mayME_962110409_1branched or may be cyclic and may have a chain length between about C1 to about C24, or about C4 to C24, C6 to C24, C12 to C24, C18 to C24, C4 to C18, C4 to C12, C6 to C24, C6 to C18, C6 to C12, C12 to C18 or C8 to C16, e.g. C1, C2, C3, C4, C6, C8, C10, C12, C14, C15, C16, C17, C18, C20, C22 or C24, or may be mixtures of any two or more of these (provided that C1 and C2 are only linear). They may also be unsaturated, for example monounsaturated, di-unsaturated or polyunsaturated. Aromatic hydrocarbons may be benzenoid hydrocarbons. They may be fused or may be linked. They may be for example naphthalene, anthracene, phenanthrene, pyrene, chrysene, corannulene or other fused hydrocarbons or may be mixtures of any two or more of these. They may be biphenyl, terphenyl, triphenylbenzene, quaterphenyl or some other linked aromatic, or may be a mixture of any two or more of these.

[0041] Any description of prior art documents herein, or statements herein derived from or based on those documents, is not an admission that the documents or derived statements are part of the common general knowledge of the relevant art.

[0042] For the purposes of description, all documents referred to herein are hereby incorporated by reference in their entirety unless otherwise statedBrief Description of the Drawings

[0043] Figure 1. A diagram showing different spatial arrangements for attachment of V to P or C, wherein V is a composition as defined herein, P is a polymer substrate and C is a carrier substrate.

[0044] Figure 2. A diagrammatic illustration of methods for attaching V to a substrate.

[0045] Figure 3. A scheme describing the process of Examples 19 and 20.

[0046] Figure 4. A scheme describing the process of Example 21.

[0047] Figure 5. A scheme describing the process of Example 27.Detailed Description

[0048] The compositions of the present invention comprise a substrate having a linker attached thereto. The linker may be attached to the substrate covalently, by coordination, chemisorption, physisorption, or by any other suitable means. The linker group serves to linkME_962110409_1the substrate to a functional moiety. The symbol V as used herein refers to the combination of the linker and the functional moiety.

[0049] The linker comprises a hydrophobic moiety, for example a hydrocarbon chain. The hydrocarbon may be straight chain, branched or cyclic or a combination of these. It may for example be methylene, 1,2-ethanediyl, 1,3-propanediyl, 1,2-propanediyl, 1,2-ethenediyl (either syn or anti), 1, 1-ethenediyl, or 1,2-cyclopropanediyl. Commonly the hydrophobic moiety, or at least a portion of the hydrophobic moiety, forms part of the direct linkage between the substrate and the functional moiety. In some instances the hydrophobic moiety may be, or may comprise, some other hydrocarbon group, e.g. a hydrocarbon ring. Examples include 1,4- cyclohexanediyl, 1,2-cyclopentanediyl, 1,4-benzenediyl and a,4-toluenediyl. It may be, or may comprise, a silicon containing group, e.g. a siloxane or silazane. The linker may comprise one or more groups attached to the hydrophobic moiety allowing it to attach to the substrate and / or to the functional moiety. These may for example be carboxyl groups, anhydride groups, acyl halide groups etc. Alternatively, there may be abstractable hydrogen atoms on the linker which allow free radical reactions to attach the linker to the substrate and / or to the functional moiety.

[0050] The substrate may be a solid substrate. It may be a polymer. It may be an organic solid. It may be an inorganic solid. It may be a salt. It may be for example silica, titania, zirconia, calcium carbonate or a similar salt. It may have a surface coating or a surface treatment or it may have no surface coating or surface treatment.

[0051] Suitable polymeric substrates include polyamides. The substrate may be an aromatic polyamide (aramid), e.g. poly-p-phenylenediamine terephthalate, an aromatic-aliphatic polyamide, e.g. hexamethylenediamine terephthalate or an aliphatic polyamide e.g. polyamide-6, polyamide-6,6, polyamide-6,10, polyamide-11 or polyamide-12. It may be a polyester, which may be aromatic, aromatic-aliphatic or aliphatic. These include polycaprolactone, polybutylene succinate, polytrimethylene terephthalate and polybiphenylene terephthalate. Other suitable polymeric substrates include polyvinylacetate, poly(ethylene-co-vinylacetate), polyolefins such as polypropylene, poly(ethylene-co-propylene) and polyethylene, and styrenic polymers.

[0052] The polymeric substrate may comprise functional groups which enable covalent attachment of the linker or of a linker-functional moiety adduct. The functional groups may be at one or both termini of the polymer chain. They may be located along the polymer chain. They may be at the termini of side-chains attached to the main polymer chain. AlternativelyME_962110409_1the substrate may have a surface conducive to non-covalent attachment to the linker. In some instances the polymeric substrate has abstractable hydrogen atoms so as to allow free radical attachment of the linker group or linker-functional moiety adduct.

[0053] The functional moiety is coupled to the linker. It may be covalently attached to the linker or may be ionically attached to the linker or may be complexed to the linker or may be attached in any other suitable manner. It may be any suitable group which comprises a semihydrophobic group and / or a hydrophilic group. In the context of this specification, a semihydrophobic group is one that is somewhat hydrophobic but possesses a degree of hydrophilicity. It is therefore intermediate in hydrophobicity between a fully hydrophobic group, such as a hydrocarbon group, and a fully hydrophilic group such as a saccharide. If coating the surface of a substrate, a semi-hydrophobic group will typically provide an advancing water contact angle of from about 45 to about 90°. By contrast a fully hydrophobic group will typically provide an advancing water contact angle of greater than about 90°, or greater than about 100, 100, 120, 130 or 135°, and a fully hydrophilic group will typically provide an advancing water contact angle of less than about 45°, or less than about 40, 35 or 30°. Advancing water contact angle may be measured by ASTM D7334-08 (2022).

[0054] Suitable functional groups within the semi-hydrophobic group include alkyl polyethers such as alkylpolyoxyethylenes, alkyl polyoxypropylenes-block-polyoxyethylenes and alkylpolyoxypropylenes, alkyl phenol polyethers and a combination of polyethylene oxide(s) and polypropylene oxide(s). By varying the lengths of the alkyl chains, the polyoxypropylene chains and the polyoxyethylene chains, the hydrophilicity of these groups may be varied within a wide range in order to suit the particular application.

[0055] Suitable hydrophilic groups may comprise polyols, saccharides, polyoxyethylenes, oligo- and poly-amines, aminosaccharides, etc.

[0056] The functional moiety also comprises one or more hydroxyl, thiol or amine functionality. In some instances more than one of these is present in the functional moiety. The presence of this group enables attachment of a suitable functional headgroup. The headgroup may be such as to confer a desired property on the composition, for example it may be, or may comprise, streptavidin, so as to enable binding to a biotinylated biomolecule. It may comprise a fluorescent group to enable visual identification. It may comprise a fluorocarbon group, e.g. a perfluoroalkyl group, a perfluoropolyalkylether group, an alkyl fluorosilicone group, or a fluoroalkyl polyhedral oligomeric silsesquioxane, so as to reduce adhesion to the surface. It may comprise a highly hydrophilic group such as a saccharide so as to modify the waterME_962110409_1contact angle and / or hydration of the surface. It may comprise an antibody, or an antibody fragment (e.g. an Fab) so as to enable selective binding to a specific antigen. It may comprise an antioxidant moiety, e.g. a hindered phenol such as a 2,6-di-t-butyl phenol group. It may comprise a UV absorber to reduce UV damage to the surface. Suitable UV absorber groups include cinnamates such as 4-methoxycinnamate, benzophenones, benzotriazoles and triazines. It may, more generally, be a group for one or more of:Improving biocompatibility and / or haemocompatibility of the composition;Enhancing affinity of the composition to water molecules;Reducing protein unfolding;Enhancing lubricity of the composition;Enhancing resistance of the composition to oxidation;Enabling site-specific recognition and / or bioconjugation and / or immobilisation of biomolecules on the composition;Enabling branching and / or crosslinking of the composition.

[0057] In some instances the substrate is inorganic. It may be a filler. It may be an inorganic filler. It may be for example calcium carbonate or silica or alumina or zirconia or titania. It may be surface treated in order to modify its hydrophilicity. For example calcium carbonate may be rendered hydrophobic by treatment with an organic acid having an alkyl chain. Silica may be rendered hydrophobic by treament with a trialkylsilyl halide such as chlorotrimethylsilane. The substrate may be particulate. It may have a mean particle size of less than about 10 microns, or less than about 5, 2 or 1 microns, or less than about 500, 200, 100, 50, 20 or 10nm, or about 1 to about 10 microns, or about 1 to 5, 1 to 2 or 5 to 10 microns, or about 10 to about 1000nm, or about 10 to 500, 10 to 200, 10 to 100, 10 to 50, 50 to 1000, 100 to 1000, 500 to 1000 or 100 to 500nm. In some instances, particularly when the treatment results in rendering the surface of the substrate hydrophobic, the treatment may be regarded as the hydrophobic moiety of the linker or a portion thereof.

[0058] In some instances a polymeric substrate may be particulate. These may be in the form of hyperbranched polymers, e.g. starburst polymers.ME_962110409_1

[0059] Compositions based on particulate fillers may be used as fillers in composite materials. Thus a particulate composition according to the invention may be used as a filler by melt processing a thermoplastic polymer such as a polyolefin, combined with the particulate composition. Alternatively, the particulate composition may be combined with precursors for a polymer, e.g. a thermoset polymer such as a polyurethane, prior to polymerisation to form a composite comprising the polymer with the particulate composition dispersed therethrough. The proportion of particulate composition in the polymer may be from about 1 to about 50% by weight, or from about 1 to 40, 1 to 30, 1 to 20, 1 to 10, 1 to 5, 5 to 50, 10 to 50, 20 to 50, 5 to 20, 5 to 10 or 10 to 20% by weight, e.g. about 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45 or 50% by weight. Composites of this type are included within the scope of the present invention. The compositions of the invention may be used as masterbatches. In this instance they may be blended with a second polymer to form a blend. The proportion of the masterbatch in the blend may be from about 1 to about 50% by weight, or from about 1 to 40, 1 to 30, 1 to 20, 1 to 10, 1 to 5, 5 to 50, 10 to 50, 20 to 50, 5 to 20, 5 to 10 or 10 to 20% by weight, e.g. about 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45 or 50% by weight.

[0060] The compositions described herein may exhibit a gradient of hydrophilicity. Thus from the surface of the substrate to the surface of the coating applied thereto, or to the functional headgroup, the gradient may be:• From hydrophobic to semihydrophobic; or• From hydrophobic to hydrophilic; or• From hydrophobic to semihydrophobic to hydrophilic; or• From hydrophobic to semihydrophobic to hydrophilic to semihydrophobic.

[0061] A suitable process for making the compositions of the invention comprises preparing a blend of the substrate, a linker precursor and a functional molecule. The substrate is as described elsewhere herein. The linker precursor is a molecule that can couple to the substrate in order to introduce the linker group into the composition. The linker may comprise a hydrophobic portion, e.g. a hydrocarbon portion. It may comprise a functional group which may be activated to couple with the substrate. The activation may be chemical activation and / or thermal activation and / or photochemical activation. In some instances therefore, the linker couples to the substrate covalently, i.e. it reacts chemically with the substrate so as to couple thereto. In other instances, the linker may attach non-covalently, e.g. by means of hydrophobic-hydrophobic interaction, complexation or similar. The blend may be heated inME_962110409_1order to facilitate incorporation of the components. It may for example be extruded, e.g. melt extruded.

[0062] In an example, the substrate is a polyolefin and the linker precursor comprises a double bond. In this example, there may be a free radical initiator, e.g. a peroxide such as dicumyl peroxide and di-t-butylperoxide. It is thought that in this case, thermal activation of the initiator gives rise to free radicals which can abstract hydrogen atoms from the substrate to generate polymeric free radicals which can react with the linker precursor to covalently attach thereto.

[0063] In another example, the substrate comprises amide and / or ester groups and the linker precursor comprises a hydrophobic portion and a functional group which is capable of being activated to react with an ester or amide.

[0064] In a further example, the substrate is a silicone rubber. Various linker precursors or combinations thereof may be used. The precursor may comprise a double bond. It may comprise hydrosilane (Si-H), silanol (Si-OH) or silamine (Si-NH2) functional groups that are attached to a hydrophobic siloxane (Si-O-Si) or silazane (Si-N-Si) backbone. In this example, a radical-mediated peroxide-based curing / vulcanizing agent, e.g. 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane or di(tert-butylperoxyisopropyl)benzene may be used. These are suitable for heat-cured rubber. The inventors hypothesise that interaction between peroxyl radicals from the curing agent and the silicone substrate occurs via hydrogen abstraction from a methyl and / or vinyl / allyl groups or via addition to the double bond on the vinyl / allyl group, if the vinyl / allyl group is present on the main polydimethylsiloxane chain of the silicone substrate. Alternatively, a platinum-based catalyst (typically Speier’s catalyst, Lamoreaux catalyst and Karstedt’s catalyst) which is thought to activate hydrosilylation reactions involving double bonds and hydrosilane groups may be used in this system and is suitable for low-temperature, rapid curing. Alternatively or additionally it is thought that the silanol (or silamine) groups can react with each other or with a hydroxyl group of a molecule bearing a polyethylene glycol (PEG) group to form siloxane (silazane) or Si-O-C bonds, respectively.

[0065] It is thought that the initial substrate-linker adduct can react with the functional molecule to form a substrate-linker-functional moiety composition. Alternatively an initially formed linkerfunction moiety composition may react with the substrate to form the substrate-linker-functional moiety composition. For example a possible mechanism is that a hydroxyl group on the functional molecule can undergo a Michael addition to an a,p-unsaturated carbonyl compound. The resulting adduct can then transesterify with an ester group in the substrate so as to bind covalently thereto. The skilled person will readily recognise that numerous variantsME_962110409_1of the above mechanisms are also feasible and may operate in specific instances. In other instances, no covalent bonds are formed. The components of the composition are then coupled by other means, e.g. hydrophobic interactions, polar-polar interactions, van der Waals forces etc.

[0066] In practice, regardless of the detailed mechanisms postulated above, the formation of the compositions of the invention may be effected by forming a dry blend of the reagents and heating to a suitable reaction temperature. Alternatively, they may be conducted in solution, followed by removal of the solvent.

[0067] The reactions discussed above may be thermally initiated. In many instances they may be conducted at a temperature above the melting temperature of the substrate. This is particularly suitable when the substrate is a thermoplastic polymer. This is not generally practicable when the substrate is an inorganic substance such as silica. Conducting the reaction in the melt allows for more efficient mixing of reagents and more even distribution of treatment throughout the bulk of the substrate. Suitable temperatures are between about 150 and about 250°C, or between ahout 150 and 200 or 200 and 250°, e.g. about 150, 160, 170, 180, 190, 200, 210, 220, 230, 240 or 250°C. These temperatures may also apply to blending components with polymers, including blending a masterbatch with a polymer. The reaction temperature will depend in part on the nature of the reaction and hence on the nature of the reactants (substrate, linker, any catalyst etc.). In some instances the reaction may occur at room temperature, or at moderately elevated temperatures, e.g. between about 50 and about 150°C, or between about 50 and 100, 100 and 150 or 70 and 120°C, e.g. about 50, 60, 70, 80, 90, 100, 110, 120, 130, 140 or 150°C.

[0068] The invention relates to a substrate having a treatment V attached thereto, e.g. on a surface thereof. V may be any one of a plurality of chemical compositions comprising W together with X and / or Y. These are described in detail below. V provides a gradient of hydrophilicity on the surface of the substrate. Two possible molecular arrangements in respect of the spatial change of the degree of hydrophobicity / hydrophilicity are illustrated in Figure 1. The substrate having V attached thereto may be a blend comprising the substrate and the components of V, or may be an association (e.g. associated by hydrophobic interactions) thereof, or may be a covalent combination thereof or may be a combination of these. In such combinations, for example the components of V are covalently bound together and V is associated non-covalently with the substrate. In another example, the substrate is covalentlyME_962110409_1bound to a linker L, which is covalently bound to a species X, and a second species Y is bound to X non-covalently, e.g. by polar-polar interaction.

[0069] The composition V may be employed as reactive precursors that are capable of being chemically bonded to the matrix of the polymer substrate P or onto the surface of an inorganic or organic carrier C or of polymer substrate P. Alternative composition V may be in the form of standalone additives that can be blended with P or C.

[0070] As reactive precursors, X and Y in the composition V may be reactive monomers or oligomers. They may be coupled to each other and coupled to P or C through the use of a covalent linker L that comprises hydrophobic component W.

[0071] As standalone additives, V may be a simple blend of W, X and Y which are individual compounds, or it may be a chemically bonded molecular compound comprising a W segment connected to X or Y or a combination of X and Y segments. Examples include W-X, W-Y, W-X-Y, W-(X-Y)m(e.g. W-X-Y-X'-Y', where m>2), (W-X)m-W, (W-Y)m-W, (W-X-Y)m-W and (W-X-Y-X')m-W. Other examples include structures of the form (W-X)m-Z, (W-Y)m-Z, (W-X-Y)m-Z, W-(X-Y)m-Z (e.g. W-X-Y-X'-Y'-Z, where m>2) and (W-X-Y-X')m-Z, where Z represents a specific headgroup attached to a repeating fundamental structure comprising W, X, and Y. In the above examples, W may be replaced by L, which is a molecule comprising W. In the examples above, m may be from about 1 to about 20, or about 1 to 10, 1 to 5, 2 to 20, 5 to 20, 10 to 20, 5 to 10 or2 to 5, e.g. about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

[0072] Composition V may comprise about 40 to about 90 mol% of W, with the remainder consisting of X and / or Y, and optionally Z. V may comprise about 40 to 80, 40 to 70, 40 to 60, 40 to 50, 50 to 90, 60 to 90, 70 to 90, 80 to 90, 50 to 80, 50 to 60, or 60 to 80 mol% by of W, e.g. about 40, 45, 50, 55, 60, 65, 70. 75. 80, 85 or 90 mol%.

[0073] If both X and Y are present, the molar ratio of X to Y may be from about 3:1 to about 1:1. It may be from about 3:1 to 2:1, 2:1 to 1:1 or 5:2 to 3:2, e.g. about 3:1, 5:2, 2:1, 3:2 or 1:1.

[0074] The molar ratio of Wto Z may be from about 10:1 to about 2:1, or about 5:1 to 2:1, 3:1 to 2:1, 10:1 to 5:1 or 7:1 to 3:1, e.g. about 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1 5:2 or 2:1.

[0075] When used to modify P or C, V may be present at about 0.1% to about 20% by weight of P or C, or about 0.1 to 10, 0.1 to 5, 0.1 to 1, 0.1 to 0.5, 1 to 20, 5 to 20, 10 to 20, 1 to 10, 1 to 5, 1 to 2 or 5 to 10%, e.g. about 0.1, 0.2, 03. 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 16,17, 18, 19 or20%.ME_962110409_1

[0076] L may be present at between 0.05% and about 5% by weight of P or C. It may be present at between about 0.1 and 5, 0.5 and 5, 1 and 5, 2 and 5, 0.05 and 2, 0.05 and 1, 0.05 and 0.5, 0.05 and 1, 0.2 and 2, 1 and 2 or 0.5 and 1% by weight, e.g. about 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5. W may be L. Therefore W may also be present in the same proportion as L. More commonly, L comprises W as well as functional groups to couple W to P or C and to X or Y. In this case the proportion of L relative to P or C is the same as that of W to P or C on a mole / weight basis, but greater on a weight / weight basis. L may be used together with X and Y as reactive precursors.

[0077] When V is coupled to P or C as described herein, it may exhibit any one or more of the following features:• It may maintain the antibiofouling performance toward biofoulants such as bacteria, funguses, viruses, proteins etc. This may be independent of corrugated / rough surface, wear, abrasion, and bulk damage of the product made thereof;• It may display long-term stability of the product made thereof in static or dynamic contact with aqueous media in the presence of common stress factors such as temperature, osmolality / salinity and pH and retain its antibiofouling performance under normal physiological conditions;• It may reduce the effect on the antibiofouling performance toward biofoulants due to low humidity or presence of an abiotic contaminant on the surface of a product made thereof. Such abiotic contaminants may include any one or more of dust, oil / grease, mould release agents, airborne particulate matter, adventitious carbon, clathrate, ice accretion and scale buildup. These contaminants may deposit on the surface if the product is exposed to ambient air and not treated in a glove box or cleanroom facility;• It may exhibit biocompatibility and haemocompatibility of a product made thereof; and• It may impede non-specific adherence of bacteria, fungi, viruses, proteins, platelets and nucleosides and other biological species or molecules onto the surface of a product made thereof.ME_962110409_1Application

[0078] The invention described herein is applicable to coating, printing, vacuum casting and painting. It is also applicable to extrusion (melt compounding) or simple dry blending. These may be followed by molding (e.g. injection molding, transfer molding, insert molding, overmolding, multi-shot injection molding and compression molding), blown film, fibre spinning and additive manufacturing. These require less costly equipment set-up and are suitable for mass production.Method 1 Incorporation of V as an additive, chain extender or prepolymer into P by blending

[0079] Blending may be achieved through various processing methods, for example melt compounding, solution mixing in water or suitable volatile non-polar, polar protic or polar aprotic organic solvent, or suspension mixing in an emulsion, commonly in the presence of a surfactant, e.g. a non-ionic surfactant. Suitable surfactants include those derived from alkyl ethers, polyol alkyl ethers and polyol polyethers.Method 2 Covalent binding / grafting of V onto P as an end group, side chain or both by chemical reaction (V-Modified P)

[0080] In this method, Pi, a polymer substrate, may comprise at least one reactive functional group F in a concentration of about 10'4to about 10 mol%. F may be present in a concentration of about 10’4to about 1, 104to 10’1, 10’4to 10’2, 10’4to 10’3, 10’3to 10, 10’1to 10, 1 to 10, 10’2to 1 or 10’2to 10’1, e.g. about 104, 5*1 O’4, 103, 5*1 O’3, 102, 5*1 O’2, 10’1, 5*10’1, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 mol%. F may be located at either or both chain ends of Pi or in a pendant group. F may be capable of bonding to a second polymer substrate, P2 which may have the same chemical structure or composition as Pi or may have a different chemical structure or composition.

[0081] Modified substrates V-modified Pi and V-modified C may be used similarly as a functional masterbatch (MB) in unmodified P2 and / or C at about 0.2 to about 40% by weight, or about 1 to 40, 2 to 40, 5 to 40, 10 to 40, 20 to 40,1 to 20, 2 to 20, 5 to 20, 10 to 20, 0.2 to 10, 0.2 to 5, 0.2 to 2, 0.2 to 1, 0.2 to 0.5, 0.5 to 1, 0.5 to 5 or 1 to 5 wt%, e.g. about 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35 or 40 wt%. The modified materials may beME_962110409_1introduced into the bulk materials by any of the blending methods described above for Method 1.Method 3 Surface modification of C with V (V-Modified C) (covalent binding: (V)m; intermolecular forces (V)n; or coordination: (V)o)

[0082] Surface modification of C may be achieved using covalent conjugation, physisorption via intermolecular forces or chemisorption via electrostatic interaction or complexation.

[0083] Surface modification may be conducted using ultrasonic homogenization / mechanical agitation of V and C in water, commonly distilled or deionised water. Under suitable conditions this forms a viscous slurry-like emulsion. The resulting modified material may be washed, e.g. with water, to remove unbound V, and then dried, for example using convection heat, induction heat, infrared, microwave, vacuum evaporation, sublimation, atomization with hot gas, centrifugation and filtration methods.

[0084] Certain examples of C have abundant functional groups, for example polarisable functional groups, available on the surface and these may facilitate the above described surface modification. Suitable groups include O-H, C=O, CO-OH, O-C-C (epoxide), CO-O-CO (anhydride), CO-H, 0-0 (peroxide), O-CO-O, C-H, C=CH2, C CH, C N, N-H, N=C=O, N=C=S, N=N+=N; C=N2, Ar-N2+(Ar = aryl group), P-OH, P-X (X = I, Br or Cl), P-H, PO3, SO3, B-OH, B-OR (R = CnH2n+i, n = 1 to 4), S-H, Si-H, Si-OH, Si-OR (R = CnH2n+i, n = 1 to 4), Si-NH, C-X (X = I, Br or Cl), Si-X (X = I, Br, Cl or F), C=N+(O“) and CEN+(O“). For unmodified inorganic carriers or those without available surface functional groups, the surface may be chemically cleaned and activated with strong acid or base prior to modification. Alternatively, a more environmentally friendly approach may employ a cold atmospheric plasma generator, low energy electron beam sterilizer or corona discharge ozone generator to activate the surface prior to surface modification. In an example a suitable substrate C is glass / ceramic microbeads. These may be hollow which provides a benefit of being light and glossy. For these, common laboratory glass cleaning formulae such as piranha solution, bleach, vinegar or oxalic acid cleaner may be used to clean and activate the particle surfaces, which are then flushed with distilled water and collected by vacuum filtration against a polymeric membrane.

[0085] Figure 2 shows a diagrammatic representation of the above methods for coupling V to P or C.ME_962110409_1

[0086] Method 1 in Figure 2 shows the blending of V with polymer P. The upper box of Figure 1 shows various combinations of W with one or more of X, Y and Z that may represent V. These may be covalently bonded, for example W-X-Y, or may be blended, for example Blend (W, X). In the case of blends, these may be associated, for example by ionic attraction, hydrophobic interaction, complexation or some other means. Other combinations than those shown may also be used, e.g. Blend (W-X, Y), in which W and X are covalently bonded and Y is blended with this covalently bonded entity. As shown in Figure 1, any of these variants of V may be blended with a host polymer P, for example by melt blending the components. The lower panel shows a detail of linker L as hydrophobic moiety W with two functional groups F. In this example, polymer P has functionalityreferred to hereafter as "ball and chain", which can interact, either covalently or by some other means, with F so as to attach linker L to P. X and Y both also have ball and chain functionality, allowing them to attach to L so as to attach indirectly to polymer P. It should be noted that the two functionalities F may be the same or may be different. Similarly, the ball and chain functionality on P may be the same as or different to the ball and chain functionality on X and Y. Group Z has a functional groupreferred to hereafter as "block and chain". This group can interact with either X or Y, either covalently or otherwise, in order to attach Z to X or Y, and therefore indirectly to P. The block and chain group may be capable of reacting with X or with Y or with the ball and chain group attached to either or both of these. It may be incapable of reacting with W or with P or with F. In some instances X and / or Y may have more than one ball and chain. In some instances Z may have more than one block and chain. In these instances V may be crosslinked. This may prevent or inhibit burying of Z into V or into P over time, e.g. it may prevent or inhibit hydrophobic recovery in cases where Z provides surface hydrophilicity.

[0087] Method 2 shows the use of a polymer Pi modified with V as a masterbatch to be combined with a second polymer P2. Thus the top panel again shows a number of combinations of Wwith one or more of X, Y and Z as described above. These may be attached to a polymer Pi as described above. As shown, V may be attached at either or both chain ends of Pi as (V)mand / or (V)oand / or may be attached as a pendant group or to a pendant chain of Pi as (V)n. If more than one V is attached to Pi they may be the same or may be different. In this instance, Pi has functionality Fi which is capable of coupling with a ball and chain functionality on the second polymer P2. Thus once V has been attached to Pi the resulting Pi-V adduct can be used as a masterbatch to combine with another polymer P2(which may be the same as or different to Pi). The attachment between the ball and chainME_962110409_1functionality on P2 and F1 may be covalent or may be some other type of attachment as described earlier.

[0088] Method 3 of Figure 2 shows the modification of C with V. This shows that (V)m(i.e. one form of V) can covalently couple with certain substrates C, whereas others, (V)ncan attach to C in other ways, e.g. by intermolecular forces such as hydrophobic interactions or polar interactions and still others (V)oby coordination forces to form V-modified C. This is commonly in particulate form and can be used as a filler in polymer Pv. This can then be used as a masterbatch for modifying a bulk polymer P2. The combining of V-modified C with Pv, e.g. to form a masterbatch, or of the masterbatch with P2, may be accomplished by any suitable method, depending on the nature of P2. If P2is a liquid (which may be the case if it is a component of a curable composite), the combining may simply require mechanical agitation. If P2is a solid, the combining may comprise melt blending, solution / suspension / emulsion blending, coextrusion or other suitable method.

[0089] In an example SPT (stearate coated precipitated calcium carbonate) is combined with polyethylene glycol distearate (PEG-DS) and a fatty alcohol polyoxyethylene ether (AEO). The stearate portion of PEG-DS (which has structure W-Y-W) and the alkyl portion of AEO (which has structure W-Y), couple with the fatty acid coating of the calcium carbonate particle due to Van der Waals interactions between the hydrophobic components. This results in an inner W layer around the particle. The ethylene oxide portions of the two additives (Y groups) are then located on the outer surfaces of the particles.Components

[0090] P is a polymeric material or its composite carrier as described below:

[0091] P may be a straight-chain, branched, cyclic or cross-linkable carbon-centred polymer or elastomer. It may be a thermoplastic polymer. It may be formed by a series of addition, condensation or cross-coupling reactions. It may be a homopolymer or a copolymer, e.g. a block copolymer, alternating copolymer, random copolymer, comb copolymer or some other type of copolymer. It may comprise a fully or partially hydrogenated alkyl, cycloalkyl and / or rigid phenyl or aromatic backbone (RH). It may have short aliphatic C2 to C18 hydrocarbon units in its main chain and / or side chain. It may have a combination of soft and hard (or crystallizable) segments so as to provide elasticity and toughness while inhibiting crack initiation and propagation in the bulk of P, thus improving the material’s abrasion and wear resistance. Suitable examples include commodity and engineering polymers such asME_962110409_1polyolefins (e.g. PE, PP, PB, EPDM, NR, COC, CBC, TPE and TPV), polyvinyl polymers (PMMA, PBA, PS, PAN, PVAc, PAA, PVA, PVC, PVDC, PTFE, PVDF, PVE, PVAm, PMVK, PGMA and PAAM), polyethers, polyacetals, polyesters (e.g. PET, PBT, PTT, PETG, PCTG, PLA, PLGA, PCL, PDO, PBS, PBSA, PBAT, PHB and PHBV), polyamines, polypeptides, polyamides (e.g. nylon 6, nylon 6,6, nylon 11, nylon 6,4, PEBA), polyurethanes, polycarbonates (e.g. BPA-PC and PTMC), polysulfides, poly(alkylene / arylene sulfide)s, polyketones, polysulfones, polyureas, polyimides, polyimines, polycarbodiimides, polyanhydrides, polyorthoesters, polyorthocarbonates, cyclic ketene acetal-containing polymers, carbohydrate polymesr, lignocellulose, polyfurans, polyfurfuryl alcohols, polythiophenes, polypyrroles, polyisocyanurates, polyoxadiazoles, resinous products from reactions of phenol, aniline, urea, formaldehyde, isocyanide, isocyanate, maleimide, melamine and glycidyl ether / epoxy, main-chain cyclic-, heterocyclic- or fused ring-based polymers, their copolymers, bulk modifications and combinations thereof; or a straight-chain, branched, cyclic or cross-linkable silicon-centred polymer or elastomer, comprising one or a combination of -Si(Rn)2-O- (siloxane) monomer unit, -SiH(Rn)-O- (silane) monomer unit, -Si(RH-OH)(Rn)-O- (silanol or carbinol) monomer unit, -Si(Rn)2-N- (silazane) monomer unit, -Si(Rn)2-O-B< (borosiloxane) monomer unit and -Si(Rn)(Rf)-O- (functional silicone) monomer unit attaching a Rf substituent to silicon, including but not limited to > C=CH-Si- (vinyl), > C=CH-CH2-Si- (allyl), CI-RH-Si-(chloroalkyl), -CH2-COO-Si- (acetoxy), -CH2-C(=CH2)O-Si- (enoxy), > C=NO-Si- (oxime), Rn-O-Si- (alkoxy), > N-Si- (amino), -OCO-Si- (carboxyl), HS-Rn-Si-(mercapto), RH-C(=CH2)-COO-RH-Si- (acryloxy), epoxidized, N-succinimidyl propionate, succinic anhydride, ethylene- / -propylene-oxide and bicycloheptenyl terminal or side chain moieties, and / or a copolymer with the aforesaid carbon-centered units. Suitable examples include commercial silicones or polysiloxanes that are categorized by their designated processing methods and / or applications, including RTV, HTV, LSR, HCR, acetoxy / neutral curing, one-part / two-part curing, post-cure / non-post-cure and silicone elastomers for sealants, pressure-sensitive / hot-melt adhesives and thermoformed products (medical-grade, foodgrade and / or body-safe). Mixtures, blends and grafts of the above polymers may also be used.

[0092] In the above. RH represents an alkyl or alkylene group. It may be C1 to C20, or C1 to C10, C1 to C6, C1 to C3, C2 to C20, C6 to C12 or C2 to C6, e.g. C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19 or C20. It may be straight chain or may be branched or may be cyclic or may be a combination of these (e.g. it may be cyclohexylmethyl). P may be a polyester or a polyamide. It may be an aromatic polyester such as PET or PBT. It may be an aliphatic polyamide such as nylon-6, nylon-12, nylon-6, 6 etc.ME_962110409_1

[0093] C is either an organic or inorganic carrier as described below.

[0094] Non-exhaustive examples of an organic carrier include resinous oxidized polyethylene wax, natural plant- or animal-derived wax-based colloidal dispersions, carbon black, graphene, graphene oxide, activated charcoal, amine or carboxylate-functionalized latex microspheres, polyhedral oligomeric silsesquioxane powders, nanocrystalline cellulose, cellulose nanofibres (CNF), microfibrillated cellulose and / or suspensions of cellulose ethers e.g. hydroxypropyl methyl cellulose, methyl or ethyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose.

[0095] Non-exhaustive examples of an inorganic carrier include unmodified or fatty acid modified precipitated or ground calcium carbonate microparticles, fumed silica, talc or mica powder, quartz, glass or ceramic microbeads (e.g. high-fracture-resistant hollow) and micro-or nano-sized reinforcing ceramic particulate fillers or refractory minerals such as clay, alumina, titania, zirconia, yttria, silicate. These may be in the form of an oxide, a sulphate, a carbide or a nitride.

[0096] Mixtures of any two or more of the above carriers may also be used.

[0097] L is a linker as described below.

[0098] If linker L is used together with X and Y as reactive precursors, L may be a bi- or polyfunctional reactive molecule or group that can form covalent bonds between V and either P or C as a side chain or an end group as well as between X and Y within composition V. L is capable of forming bonds by different methods depending on the functional groups present. These methods include addition, condensation, metathesis and cross-coupling reactions that lead to covalent bridges including C(sp3)-C(sp3), C(sp3)-C(sp2), > C=C<, -O- (ether), -COO-(ester), -OCOO- (carbonate), -CO-O-CO- (anhydride), -CO- (carbonyl), -C(-ORH)2-O- (ortho ester), -C(ORH)2- (acetal / ketal), -O-O- (peroxyl), > N- (sec- or tert-amine), -N(RH)2+- (quaternary ammonium), -N=N- (azo), > C=N-N=C< (azine), > N-CO- (amide), > N-COO- (carbamate ester or urethane), -CO-NRH-CO- (carbonyliminocarbonyl), -CO-NRH-CO- (imide), > N-CO-N< (urea / carbamide), -N=C< (imine), > N-CRH=C< (enamine), > N-CRH=CRH-C(=O)-(ketoenamine), > N-C(=NH)-N< (guanidine), -NH-N=C< (hydrazone), -CO-NH-N=C< (acylhydrazone), -CO-S- (thioester), > N-CS- (thioamide), > N-CS-N< (thiourea), -C(=N-OH)-(oxime), > NO- (alkoxyamine), -N=P< (phosphazene), -P- (phosphine / phosphorane), -PO-(phosphine oxide), -PO2- (phosphinate), -PO3- (phosphonate / phosphite), -PO4- (phosphate), -SO- (sulfoxide), -SO2- (sulfone), -SO2-O- (sulfonate), -O-SO-O- (sulfite), -SO4- (sulfate), -S-ME_962110409_1(sulfide), -S-S- (disulfide), > Si(OH)-O- (siloxane). Other examples of covalent bridges include oxazole, triazole, p-thiol-propionate, maleic / citraconic acid-amide, cis-aconityl-amide, phosphoramidate, phosphonamide, phosphoro(di)thioate, carbodiimde, boroxine, boronic ester, borazine, dioxaborolane, 1,4-dioxin, phenazine, triazine, squaraine, cyanuric amide, thiocarbamate, sulfonium, trithiocarbonate, thiourethane, thiosulfonate, diselenide, sulfonamide and covalent linkages derived therefrom. Either a strong, bulk degradable (hydrolytically, thermally, photochemically labile or acid / base-sensitive) or surface-erodible bond linkage may be used, depending on the intended application, product service lifetime and other physical properties of the product made thereof. For example, carbamate, oximecarbamate, oxime-ester, enamine-one and other vitrimer-based dynamic covalent linkages with self-healing properties may be used in applications requiring self-repair of microscopic structural damages of the bulk polymer substrate. In contrast, the use of hindered urea linkages, such as a 1-terf-butyl-1-ethylurea bond, can reversibly dissociate to bulky amines and isocyanates, the latter of which may further hydrolyze into amines, thus preferentially driving the degradation of the composition V. When long term stability in contact with an aqueous medium is required, non-hydrolyzable linkers are preferred.

[0099] W is a hydrophobic component of composition V, as described below. In particular, W is a portion of linker L. It may contribute to low surface tension of composition V. W may exhibit a critical surface tension in the range of about 18 to about 32 mN / m, or about 18 to 30, 18 to 25, 18 to 21, 20 to 32, 25 to 32, 29 to 32, 20 to 30, 20 to 25 or 25 to 30mN / m, e.g. about 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 or 32mN / m.

[0100] Covalent linker L may be regarded as a functionalized derivative of W, which incorporates W into composition V. L includes a spacer group derived from W. W may comprise a group selected from a cyclic, linear or branched saturated, mono- or polyunsaturated hydrocarbon unit, optionally of mixed carbon lengths between C2 and C24, for example those obtained from a petroleum refinery such as paraffin, Fischer-Tropsch wax, a microcrystalline wax, a polyethylene wax, an a-olefin, mineral oil, squalene, squalene or petroleum jelly. W may comprise a naturally occurring wax. Non-limiting examples include beeswax, linoleum, lanolin, laurel, shellac, ozokerite, carnauba, candelilla, jojoba, bayberry, rice bran, soy, sunflower, rapeseed, coconut, avocado, almond, argan peat, ouricury, montan and sugarcane. W may comprise a biodegradable wax such as Deurex, a gum rosin, a fatty acid amide, a fatty alcohol, a fatty acid alkyl ester (e.g. octyl stearate, decyl oleate, isopropyl isostearate, isopropyl palmitate and dialkyl dimer dilinoleate) shea butter, cocoa butter, a plant (seed) oil or an animal fat with abundant triglycerides and fully saturated, mono- or poly-ME_962110409_1unsaturated fatty acids, such as stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, oleic acid, linoleic acid, linolenic acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid and docosapentaenoic acid, a terpenoid, such as camphor, pinene, limonene, caryophyllene, humulene, linalool, borneol geraniol, citronellol and myrcene, a carotenoid, such as lycopene or carotene, a hydrophobic steroid such as cholesterol, lanosterol, zymosterol, ergosterol, estrogen or testosterone, dimethicone, caprylyl methicone, a cyclomethicone, 1 to 3 covalently connected rigid aromatic monomers, such as biphenyl, a planar fused ring unit, such as naphthalene, an alkyl-aryl ketone monomer, a vinyl monomer containing a pendant aromatic unit, such as styrene and 2-phenyl acrylate, an aromatic dicarboxylic acid / anhydride, such as phthalic acid / anhydride and naphthalenedicarboxylic acid / anhydride, dimethyl or phenyl methyl oligosiloxane, cyclosiloxane, lower fluorocarbons of (-CF2-)3to8, and liquid crystalline mesogens with rod-like or disc-like configurations. It is thought that these latter may impart conformational restriction, steric hindrance and mechanical integrity such that X and / or Y attached thereto may be accessible to more water molecules leading to a faster wetting dynamics and a stronger hydrogen bond network while counteracting the effect of compressive force to impede the deformation and total collapse of V due to the precipitation and sorption of a foulant or a solute (either hydrophilic or hydrophobic) under static conditions. This may favour the desorption of foulant or solute with moving water.

[0101] In some instances, where blending incorporates one or more of the components of V, W may be the same as L or may comprise no functional groups or may only comprise one functional group.

[0102] The Examples provided in this specification show representative forms of L and W. In these examples, selected molecular covalent linkers (L) include MAH (maleic anhydride), ITA (itaconic acid), FA (fumaric acid), PC (propylene carbonate), MIPA (monoisopropanolamine), DEIPA (diethanol isopropanolamine), TIPA (triisopropanolamine), C10-DA (1,10-decanedicarboxylic acid), PHPS (perhydropolysilazane), PMX (silanol fluid or OH-terminated polydimethylsiloxane) and CL (caprolactam). Within these examples, L in general has a functionality of at least two and W is part of L. In Example 2, L is ITA, having structure HO2C-CH2-C(=CH2)-CO2H. In this structure, L contains both W, which is CH2-C(=CH2), and two carboxylate groups (-CO2H) which are capable of forming ester (-COO-) or amide (-CONH-) linkages by reaction with hydroxyl or an amine functional group present in X, Y, P or C. Similarly, in Examples 1 and 3, MAH and FA, contain a similar W, i.e. -CH=CH- (cis- and trans-respectively). In Example 10, a combination of linker molecules, including PC, MIPA, DEIPAME_962110409_1and TIPA, are used. The chemical structure of PC is (CH3-CH-CH2)-O2CO, and those of MIPA, DEIPA and TIPA are in the general form [CH3-CH(OH)-CH2]m-NHn(m = 1 to 3; n = 2 to 0, m+n=3). These have functional groups: carbonate, hydroxyl and amine groups. W, in the form CH2-CH-CH3, is common to each of these as a hydrocarbon group for all of these examples of L. In Example 17, there are two linkers L: CL and C10-DA. In these, W is a longer aliphatic hydrocarbon chain, C5 and C8, in CL and C10-DA respectively. In Example 26, W becomes a polysilazane and a polysiloxane chain in the case of PH PS and PMX respectively.

[0103] As discussed above, L has both W (a hydrophobic, optionally non-functional group) and functional groups which are capable of forming polar covalent bridges. Guanidine is one example of a covalent bridge formed between W and X / Y or between W and P / C in the form of > N-C(=NH)-N<. Squaraine (> NH-C4C>2-NH<) is another example. When L reacts with X or Y, the polarity of the linkage may contribute toward X or Y segments rather than W.

[0104] In some instances, other than condensation and free radical addition, the covalent linker L is an enolisable compound or a pre-activated enolate surrogate comprising a functional group with an acidic a-proton (typically ranging from pKa 10 to 30) or a masked nucleophilic centre. This configuration includes, but is not limited to, a carbonyl group or other electron-withdrawing groups (EWG) where acidity follows the descending order of: nitro, 1,3-dicarbonyl, aldehyde, ketone, nitrile, ester, carbamate, and amide. Specifically, L may contain an a-methylene carbonyl (-CH2-CO-), a propane-2-one-1,3-diyl (-CH2-CO-CH2-), an acetyl (CH3-CO-), an acetoacetyl (CH3-CO-CH2-CO-) ora nitroalkyl group (-CH2-NO2). The presence of at least one a-proton adjacent to the carbonyl or nitro group allows L to act as a nucleophile via tautomerisation to an enol (-C=C-OH) or preferably, via formation of some intermediates by deprotonation which are categorized as: (1) an enolate (-C=C-O_-C_-C=O), where the counterion is usually an alkali or alkaline earth metal (such as Li+, Na+, K+, Mg2+); (2) a nitronate (-C=N+(O')2 -O-NO2); (3) a metallo-enolate (-C=C-O-M M+-C“-C(=O)), where M is an organometallic moiety based on boron (-BG2 or -Bpin), tin (-SnGs), zinc (-ZnG), titanium (-TiGs), copper (-CuG), palladium (-PdG) and zirconium (-ZrGs), optionally stabilised by coordinating ligands such as phosphines or nitrogen heterocycles; (4) an enolate surrogate (masked nucleophile), such as an enamine (-C=C-NG2 -C“-C=N+G2), a silyl enol ether (or silyl ketene acetal) (-C=C-OSiG3 -C“-C=O+-SiG3) and aza-enolate (or hydrazone) (-0=0-N-G -C“-C=N+-G), where G is independently selected from 01-04 alkyl, alkoxyl, tert-alkyl, isoalkyl, cyclic 05-06 alkyl (such as cyclopentadienyl), phosphino (such as triphenylphosphino) or aryl (such as 2,2'-bipyridyl) groups. Bpin is specifically referred as pinacol boronate.ME_962110409_1

[0105] These species subsequently attack an electrophilic carbon, silicon, phosphorus or sulfur atom located on the substrate P or C. These electrophilic sites are categorised as: (1) leaving group-activated sites: C-LG, Si-LG, P-LG or S-LG, where LG is an effective leaving group such as I, Br, Cl, N2+, OSO2CF3, OSO2C6H4CH3, OSO2CH3 and OCOCF3, yielding a-alkylated, a-silylated, a-phosphorylated or a-sulfonated adducts; (2) unsaturated electrophiles: C=O, C=N, C=N, C=S, S=O, N=C=O, N=N and nitro-containing carbonyls (such as -C(=O)-NO2 and -C(=O)-CH2-NO2), yielding p-hydroxy (aldol), p-amino, p-imino (aza-aldol), P-mercapto, p-sulfinyl, p-amido, p-hydrazino and p-nitro (nitro-aldol or p-nitro alcohol) adducts, respectively; (3) cyclic electrophiles: carbonyls within cyclic anhydrides or imides, where nucleophilic acyl substitution triggers ring opening to yield p-carboxyl or p-amide adducts; and (4) reactive activated species: Michael acceptors (EWG-activated C=C or C=C, such as conjugated nitroalkenes) or epoxides, resulting in p-alkyl, p-substituted nitro or y-hydroxy adducts. For additions to unsaturated electrophiles, the resulting p-functionalized intermediates may undergo dehydration or elimination. This yields a,p-unsaturated compounds suitable for further tandem reactions with X or Y which can be derived from primary or secondary amines, thiols, alcohols, carbon-centered nucleophiles (such as compounds functionalised with malonates, nitromethyl groups or Grignard reagents), 1,3-dienes (such as compounds functionalised with 1,3-butadiene, cyclopentadiene or Danishefsky’s diene), 1,3-dipoles (such as compounds functionalised with azides, ylides, nitrile oxides, nitrosimines, carbonyl oxides, nitrones or diazoalkanes) and free radical precursors (such as compounds comprising unsaturation, peroxides, halides, xanthates, a-keto esters / ketones, organoselenides or stable nitroxide radicals, e.g. TEMPO or derivatives thereof, capable of generating radical species via homolytic cleavage).

[0106] X is a semi-hydrophobic component, as described below. X may exhibit a critical surface tension in the range of about 30 to about 40 mN / m, or about 30 to 35, 35 to 40, 33 to 37, 32 to 40 or 32 to 35mN / m, e.g. about 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 or 40mN / m. X may exhibit a critical surface tension greater than that of W. The critical surface tension difference between X and W may be at least about 5, 10 or 15mN / m, or from about 5 to about 15, 5 to 10, 10 to 15 or 3 to 7mN / m, e.g. about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15mN / m.

[0107] X may be capable of producing a gradient transition interlayer between W and Y. X may be an emollient. X may be for example a polyol polyester, such as ethoxylated alkyl glyceride (trade names include Glycerox®, Crovol®from Croda and Cremophor® from BASF), palmitoyl ethanolamide, a hydroxylated, ozonated, sulfonated / sulfated, alkoxylated, epoxidized, di- or poly-carboxylated (through reaction with maleic acid, fumaric acid, muconicME_962110409_1acid, itaconic acid, adipic acid, succinic acid, malonic acid, 2,5-furandicarboxylic acid, citric acid, their anhydrides or derivatives) or partially hydrolyzed glyceride of plant (seed) origin. Suitable such glycerides include soybean, coconut, cottonseed, linseed, rapeseed, tung, sunflower, palm, maize, corn, rice bran, peanut, sesame, mustard, wasabi, horseradish, camellia, moringa, pumpkin, neem, perilla, safflower, olive, echium, hemp, meadowfoam, Passiflora, macadamia, borago, walnut, hazelnut, chokeberry seed, peach kernel, wild rose, raspberry. It may be a gyceride inherently rich in hydroxy or epoxy fatty acids or their esters, such as ricinoleic acid (castor), 15-hydroxy-linoleic acid (oat seed), nebraskanic acid (Chinese violet cress), dimorphecolic acid (Dimorphotheca seed), vernolic acid (ironweed), cutin and suberin, melanin, humic acid, fulvic acid, an oxidized polyolefin, any or all of which is available in powder or emulsion form with commercial brands such as Poligen®, Liquilube®, Lakewax® and Michem®, API 188, an alkanolamine, an alkanolamide, an alkyl phenol, an alkyl phenol ethoxylate, such as nonyl phenol ethoxylate, cashew nutshell liquid derived cardanol-, cardoland 3-pentadecylphenol-based polyoxyethylene ether, an alkoxylated or butynediol ethoxylate-modified oligosiloxane, an aminosilicone, a polymer bearing pendant N-hydroxyphthalimide, glyceryl stearate, lactone / lactam and lipid penetration enhancing moieties, such as laurocapram, iminosulfurane, muscone, N-octyl pyrrolidone and their structural analogs, ethoxylated acrylate ester, citrate ester, cholesterol p-D-glucoside, alkyl dimethylamine oxide, a glycolipid such as mannosylerythritol lipid, sophorolipid, rhamnolipid, cellobiose lipid, trehalolipid, a lipopeptide such as surfactin, an exopolysaccharide such as emulsan, a sphingolipid with an N-acyl and serine linker such as sphingosine, ceramide and sphingomyelin, a phospholipid with a glycerol-phosphate ester linker such as lecithin, cephalin, cardiolipin or their structural analogs, saponin, or a water-soluble / dispersible thermoresponsive lower critical solution temperature (LCST) polymer that features a cloud point in the range from about 30°C to about 40°C (or from about 40 to 35 or 35 to 40°), for example around the physiological temperature of 37°C and that comprises vinyl monomers such as 2-oxazoline, 2-isopropyl / ethyl-2-oxazoline, caprolactam, pyrrolidone, piperidone, piperidine, azacyclooctanone, 2-ethyl / n-propyl-2-oxazine, methyl vinyl ether, isobutyramide, N-acryloyl-N’-propylpiperazine, N-vinylcarbazole, (hydroxymethyl)oxetane, 1-vinyl-2-(hydroxymethyl)imidazole, oligo(ethylene glycol) methyl ether methacrylate, 2-aminoethyl(meth)acrylate, 2-dimethylaminoethyl(meth)acrylate, N, N-dimethyl aminoethyl methacrylate, N-alkyl(meth)acrylamide, N-ester-(meth)acrylamide and N, N-dialkylacrylamide or their various N-substituted acrylamide derivatives by adjusting the hydrophobicity of substituents on the nitrogen atom on the side chain, such as N-isopropyl(meth)acrylamide, N-ethylacrylamide, N-cyclopropylacrylamide, N-n-propylacrylamide, N-(2-ME_962110409_1hydroxypropyl)(meth)acrylamide, N-2,2-difluoroethyl)acrylamide, N-acetoxyethyl acrylamide, N-acryloylglycine, N-acryloylglycine methyl ester, N-acryloylglycine ethyl ester, N, N-ethylmethylacrylamide, N, N-diethylacrylamide, N, N-bis(2-methoxyethyl)acrylamide, N-acryloylpyrrolidine, N-acryloylpiperidine and N-acryloylmorpholine, and their structural analogs, derivatives and combinations thereof. To facilitate tuning of the zeta potential of the polymer substrate P, positively charged vinylamine, or N-vinylformamide, N-vinyl t-butylcarbamate, N-vinylphthalimide or N-vinylacetamide which are convertible to vinylamine by hydrolysis with a Bronsted acid, may be employed as a co-monomer to polymerize with the aforesaid vinyl monomers and may provide an electrostatic balance of the negatively charged components at majority in Y wherever deemed necessary.

[0108] Y is a hydrophilic component as described below. Y may exhibit a critical surface tension of about 40 mN / m or above. It may exhibit a critical surface tension of at least about 45, 50, 55, 60, 65 or 70, or between about 40 and 80, 50 and 80, 60 and 80, 40 and 70, 40 and 60, 40 and 50, 50 and 70 or 50 and 60mN / m, e.g. about 40, 45, 50, 55, 60, 65, 70, 75 or 80mN / m. Y may exhibit a critical surface tension greater than that of X. The critical surface tension difference between X and Y may be at least about 5, 10, 20, 25 or 30mN / m, or from about 5 to about 40, 10 to 40, 20 to 40, 30 to 50, 5 to 30, 5 to 20, 5 to 10, 10 to 30, 10 to 20 or 20 to 30mN / m, e.g. about 5, 10, 15, 20, 25, 30, 35 or 40mN / m.

[0109] Y may be a macromolecular crowder. It may be a humectant capable of water / moisture uptake and hydration at pH range between about pH 5 and about 9 (or between about pH 5 and 7 or 7 and 9 or 6 and 8, e.g. at pH 5, 6, 7, 8 or 9). It may be capable of nonspecific binding of biological factors and biotic substances. Y may be selected from a carbohydrate polymer or polysaccharide such as dextran, Ficoll®, glucan, glycogen, (alkyl)polyglucoside, hydroxyalkyl starch, carboxylated starch, hydroxyalkyl cellulose, hemicellulose, xylan, alginate, pectin, agar, xanthan, gellan, pullulan, low-molecular-weight hyaluronan, N-carboxymethyl or anhydride-modified polyglucosamine (chitosan or chitin), glycosaminoglycan, gum Arabic, guar gum, tragacanth gum, kondagogu gum, cashew gum, konjac-glucomanan, locust bean gum, fenugreek seed gum, flaxseed gum, karaya gum and polygalacturonic acid, a sulfated polysaccharide, such as dextran sulfate, chondrotin, keratan, heparin, carrageenan, ulvan, fucoidan, laminarin, dermatan, galactofucan and galactan, honey, a starch-modified polymer derived from polymers including polyacrylate, carboxylated butadiene nitrile and polyacrylamide, a polyhydroxyalkanoate, such as poly(3-hydroxy butyrate) and its copolymer with 3-hydroxyvalerate and / or with 4-hydroxybutyrate, an alkali metal salt-forming acid polymer, such as carbomer, poly(thio)phosphate orME_962110409_1polyphosphonate and their ester derivatives, polyphosphonate, pentosan polysulfate, poly(4-styrenesulfonate), poly(4-vinylbenzoate), poly(acrylate-co-maleate), poly(metaphosphate), polyepoxysuccinate, poly(4-methacryloyloxyethyl trimellitate), poly(itaconate), polymandelide, poly(vinyloxy-4-butyrate), poly(2-hydroxybutanoate), poly(2-hydroxy-3-phenylbutanoate), poly(acrylamide-2-methyl-propane sulfonate), poly(3-sulfopropyl methacrylate), polyvinylsulfate and lignosulfonate, poly(ethylene citramide), poly(ethylene malamide), poly(ethylene tartaramide), polyethyleneimine, poly(N-vinylimidazole), a polyelectrolyte containing multiple sulfate, sulfonate, phosphate, phosphonate, phosphite, nitrate, chlorate, perchlorate anions or a combination of these groups, a quaternary ammonium compound (quat), an ammonio methacrylate copolymer for example with ethyl acrylate, methyl methacrylate, methacrylic acid and / or styrene (traded under the tradename Eudragit®), a polyquaternium, poly(crotonobetaine), a polyetheramine (traded under the tradename Jeffamine®), a poly(amino acid) such as polylysine, polyproline, polyglutamate, polyaspartate, polytartarate and polycarnitine, a peptidomimetic polymer such as polypeptoid, poly(P-peptoid) and their derivatives, polyethylene glycol, poly(ethylene glycol)-block-poly(propylene glycol), glycerol ethoxylate / propoxylate, neutral, anionic or cationic polyacrylamide, a poloxamer (traded under tradenames Pluronic® and Tetronic®), polyhydroxyethylmethacrylate, hydrophilized poly(ether)sulfone, polyhydroxyurethane, polyorganophosphazene, an alkyl ether such as the chemicals traded under tradenames Triton®, Genapol® and Brij®, a polyol alkyl ether such as the chemicals traded under tradenames Span®, Tween® and Nonidet®, polyglycerol or its derivatives, an alkyleth sulfate, an alkyl (polyoxyethylene / polyglycoside) sulfosuccinate, polyvinylalcohol, fully- or partially-hydrolyzed polyvinylacetate, an aliphatic carbonyl polymer that is copolymerized with monomers such as of p-dioxanone, trimethylene carbonate, 5-hydroxy-trimethylene carbonate, 2-hydroxybutanoic acid, propiolactone, caprolactone, b-valerolactone, lactic acid, glycolic acid and their derivatives, a water-soluble globular protein such as gelatin, casein, albumin, hemoglobin, lactoglobulin, swine gammaglobulin, lysozyme, a double helical deoxyribonucleic acid, such as B-DNA, or combinations thereof.

[0110] Y optionally:(i) comprises kosmotropic (surrounding water structure-making) building blocks (optionally in high proportion) with -OH, -CH2-OH, -CH2-CH2-OH substituents that can act as both a hydrogen bond donor and hydrogen bond acceptor, carbonyl groups, ether oxygen atoms and charged moieties. In descending order of kosmotropic activity and spatial extent of hydration shell formation these include:ME_962110409_1carboxylate, phosphate, phosphonate, sulfate, sulfonate, NH-bearing amines or amides and quats. It is thought that these lead to a stronger excluded volume and soft repulsive effect towards foulants or solutes while suffering fewer interferences from chaotropic counterions; and / or(ii) retains tightly bound, non-freezable water that freezes below about 0°C, or below about -10, -20, -30, -40, -50, -60, -70, -80, -90 or-100°C; and / or(iii) exhibits hyperbranched molecular configurations and random tree-like spatial growth. This may increase its surface coverage density by terminating a number of dangling terminals made up similarly of Y, Y-Z and Z; and / or(iv) produces an elastic, non-collapsible and high aspect ratio brush-like molecular topology with rapid wetting and small contact angle hysteresis upon dynamic contact with an aqueous medium. Quat-bearing polymers, such as those containing choline moieties, may be used to improve the solubility of Y in water with the benefit of a low charge density and less tendency to associate with oppositely-charged foulants or solutes. These are only recommended for a small amount because the bulky cation is rather weakly hydrated.

[0111] Z is a functional headgroup as described below.

[0112] Z may serve one or more of the following functions:(1) improving the bio- or hemo-compatibility of V. This may be achieved by selecting as Z a polar headgroup mimic of a sphingolipid or a phospholipid, such as glycerol, ethanolamine, serine, glucose, galactose, higher glycan derivatives, inositol, phosphate, sialic acid, choline and phosphocholine, or a combination thereof;(2) enhancing affinity towards water molecules and thereby resistance to protein adsorption / aggregation and hydrostatic pressure. This may be achieved by selecting as Z a humectant or a naturally occurring osmolyte or piezolyte, such as a methylamine oxide of formula -RH(CH3)2N+O' (structurally similar to trimethylamine N-oxide), or isosteric analogs of an alcohol, such as -RH(CH3)2C-OH (structurally similar to t-butyl alcohol) or -RH(CF3)2C-OH (structurally similar to hexafluoropropan-2-ol) or an amine, -RH(CH3)2C-NH2 (structurally similar to triethylamine and isobutylamine) or other compounds such as a polyhydric compound / polyol, a sugar alcohol, an a-, - or poly-hydroxy acid, an amino acid or a zwitterion, including trehalose, 2-sulfotrehalose, D-glucopyranose, erythritol, trimethylopropane,ME_962110409_1monopentaerythritol, dipentaerythritol, sorbitol, ribitol, arabinitol, xylitol, mannitol, pinitol, galacticol, ononitol, maltose, fructose, fructan, sucrose, tagatose, psicose, mannose, lactose, sucralose, lactitol, isomalt, hydrogenatated starch hydrolysate, glycine, carboxybetaine, proline, ecotine, carnitine, isoleucine, creatine, taurine, alanine, valine, y-aminobutyric acid, N-acetylhistidine, arginine, lysine, homarine, sarcosine, glutamine, glutamate, aspartate, diglycerol phosphate, di-myo-inositol-1,1'-phosphate, cyclic-2, 3-diphosphoglycerate, floridoside, glucosylglycerol, dimethylsulfoniopropionate, mandelic acid, glycolic acid, lactic acid, citric acid, malic acid, tartaric acid, pyrrolidinecarboxylic acid, p-hydroxybutanoic acid, betaine salicylate, gluconolactone, lactobionic acid, maltobionic acid, panthenol, butylene / propylene glycol, urea, allantoin or a compound end-capped with carboxylate, carbamide, imidazole, pyrazole, pyrrole or their derivatives;(3) exerting add-on resistance to protein unfolding. This may be achieved by selecting as Z a protein stabilizer or a chemical chaperone, for example a polyamine such as spermine, spermidine and putrescine, a sulfur-containing amino acid, such as cysteine, methionine or their ester or amide derivatives, 4-phenylbutyric acid, a hydrophilic bile acid, such as ursodeoxycholic acid and tauroursodeoxycholic acid;(4) enhancing the lubricity of the topmost surface layers spatially occupied by Y. This may be achieved by using a chaotrope or a hydrotrope, that is weakly hydrated and may contain a large but polarizable charged moiety, hindered with phenyl, short aliphatic, ring-opened C1-C3 or cyclic N-alkyl substituents such that the headgroup Z tends to form clathrate hydrates surrounding its hydrophobic components, accompanied by a higher mobility of water near the topmost surface. This may result in a smaller hydrodynamic shear force needed to remove foulants or solutes from the surface of P. Examples of Z include sulfobetaine, nicotinamide, dodecaborate, polyoxometalate, a compound end-capped with isothiocyanate, anionic units of sulfonate, thiosulfate, tosylate and fluorophosphate and positive units of triazolium, pyridinium, anilinium, dimethylsulfonium and dimethylsulfoxonium units, a cyclic amine, such as quinuclidine, pyrrolidine, piperidine, piperazine, morpholine and dimethylcyclohexylamine, an O-alkylated heterocyclic N-oxide, a bis(pyridinium), a naturally occurring alkaloid, such as morphine, strychnine, quinine, ephedrine and nicotine, lycobetaine and their structural analogs and derivatives;(5) enhancing the resistance to oxidative stress. This may be achieved by the use of ascorbic acid, various compounds belonging to the classes of phenolics, flavonoids, anthocyanins, aglycones or carotenoids, including hydroquinone, catechol, tinnevellin, arbutin, koji acid,ME_962110409_1ellagic acid, 4-(4-hydroxyphenyl)-2-butanol, tranexamic acid, salicylic acid, 5,5’-dipropyl-biphenyl-2,2’-diol, resorcinol, urushiol, bakuchiol, hydroxycinnamic acid, ferulic acid, Licochalcone A, pyrogallol, vanillin, resveratrol, quercetin, baicalein, kaempferol, myricetin, naringenin, curcumin, catechin, tannin, uric acid, purine, caffeine and their structural analogs, N-aryl / alkyl benzamides, p-hydroxy-substituted meso-tetraphenylporphine, an electronwithdrawing chloro- or nitro-substituted phenolic compound, some isolated metabolite compounds, such as astaxanthin, lutein, zeaxanthin, kahalalide F, mycosporine, bacteriorubin, pannarin, scytonemin and curacin A, and several classes of Maillard reaction heterocyclic products including furan, furanone, pyranone, pyrrole, thiophene, pyrazine, acylpyridine, alkylpyridine and oxazole;(6) enabling site-specific recognition and / or bioconjugation / immobilization with fluorescent tags, biomarkers, growth / inhibition factors, signalling molecules, preservatives, drugs and / or redox-active molecules. This may be achieved by use of an intermediate terminated with a reactive functional group such as amine, aldehyde, carboxylic acid, maleimide, thiol, N-hydroxysuccinimide (NHS) or sulfo-NHS ester, tosylate ester, methanesulfonyl acrylate, alkyne, azide, dibenzocyclooctyne, trans-cyclooctene, hydrazide, silane, boronic acid, biotin, nickel-nitriloacetic acid, a,p-unsaturated carbonyl unit, a peptide protecting agent, such as 9-fluorenylmethoxycarbonyl and tert-butoxycarbonyl, a protein binding agent, such as nitrocellulose and dopamine, an enzyme activity inhibitor, such as tris(hydroxymethyl) aminomethane, a non-enzymatic cell detachment agent / metal chelator, such as ethylenediaminetetraacetic acid, a light sensitizer, such as chlorin, porphyrin and phthalocyanine, a colorimetric sensor, such as spiropyran, or a host-guest cavity-type compound, such as cyclodextrin; and(7) enabling side-branching and moderate crosslinking of V near the topmost surface (i.e. that surface remote from P or C). This tends to form a re-entrant morphology which may serve to filter foulants or solutes and minimize their intra-diffusion into the bulk and as an occlusive to trap the absorbed moisture while preventing immediate water loss from inner layers. With this topology, the topmost surface is stiffened at static or low-shear condition which makes itself desirable for avoiding initial adsorption in either dry or wet environment. The loosely associated inner layer structures are dramatically and rapidly disrupted and aligned under shear, causing a steep drop in viscosity so that smaller foulants or solutes, even mechanically interlocked within inner layers, can be removed easily under fluid flow or dry sliding process. Also, moderate crosslinking near the topmost surface may expedite the recovery of the topological structure upon resumption to static condition. This may be achieved by the use ofME_962110409_1a vinyl monomer containing a free radical / heat-activatable vinyl double bond, such as divinylbenzene, triallyl isocyanurate, N, N’-1,4-phenylenediacrylamide, 3,5-bis(acryloylamido)benzoic acid, 2,6-bisacryloylamidopyridine, ethyleneglycol dimethylacrylate, N, O-bismethacryloyl ethanolamine, N, N'-bis(acryloyl)cystamine, N, N’-methylenediacrylamide, 1,4-diacryloyl piperazine, pentaerythritol triacrylate, trimethylolpropane triacrylate, or a hydrogelation-inducible precursor, such as tetraethoxylsilane and 1,4-bis(triethoxysilyl)benzene, or combinations thereof, optionally of mixed hydrophilicity / hydrophobicity and steric structure.

[0113] The hydrophilic components in X and Y may capture water molecules from ambient moisture or condensed water vapor or an aqueous medium wetting a substrate. This may result in creation of a number of hydration domains with tightly bound water molecules, as shown in Figure 1.

[0114] Binding of linker L with substrate P or C gives rise to a hydrophobic interlayer at the anchoring point and more hydrophobic domains between X and Y, where air voids / pockets may be trapped at a molecular level. These spaces may therefore offer a secondary barrier to intrusion of water molecules and avoid penetration of some polar foulants or solutes deeper into the top surface layers of the composition V and their further interactions with the substrate.

[0115] In general, the antibiofouling composition, V, is derived from selection of a combination of substances that contain a hydrophobic anchor (W) and an amphiphilic to hydrophilic surfactant segment (X and / or Y) that is entropically flexible, shear-thinning and comprises water affinity groups. These are configured to form a steric barrier i.e. maintain an excluded volume that repels foulants through a hydration-independent or enhanced hydration mechanism. The water affinity groups are capable of entrapping water molecules to form a number of discretely spaced hydration / solvation shells. For example, PEG-containing surfactants are one useful embodiment due to their wide market accessibility and non-ionic nature. Poly(2-oxazoline) and polyglycerol are two typical examples of direct backbone mimics of PEG. Alternative approaches to PEGylation include PVPylation, PASylation, XTENylation, PSarylation, ELPylation, hyperglycosylation, protein fusion and incorporation with polyacrylamide or zwitterionic polymers containing balanced charges with sulfobetaines, carboxybetaines, phosphorylcholines, cysteines and D-penicillamines that exhibit the required flexibility and shear-responsive characteristics.

[0116] The composition V may additionally comprise a stabiliser, e.g. an antioxidant. It may be a phenolic antioxidant, e.g. a hindered phenol antioxidant such as Irganox® 1010. It mayME_962110409_1also comprise common additives for altering the physical / chemical properties or aiding processing of the substrate P, such as filler, colour masterbatch, plasticiser, rheology modifier, impact modifier, antistatic, slip agent, mould release agent, antiblock, wetting agent, dispersant, diluent, defoamer, flame retardant, scratch and mar resistance agent, matting agent, gloss enhancer, optical clarifier, adsorbent, fragrance, hardener, primer, accelerator and curing co-agent.

[0117] Enrichment of composition V may be additionally achieved by two approaches: (1) converting the substrate P into either an open or closed foam structure by adding a blowing agent, such as azodicarbonamide, sodium bicarbonate / citric acid, hexahydro-1, 3, 5-trinitroso- 1.3.5-triazine and 4,4'-oxybis(benzenesulfonylhydrazide), into V, thereby concentrating it within cell walls; or (2) adding a nucleating agent, such as talc, kaolin clay, calcium carbonate, sodium 2,2'-methylene-bis-(4,6-di-t-butylphenylene)phosphate, sodium benzoate, disodium bicyclo[2.2.1]heptanedicarboxylate, disodium hexahydrophthalate, dibenzylidene sorbitol and 1.3.5-triazine-2,4,6-triol, into V to boost the degree of crystallinity by increasing the number of nuclei while diminishing the size of spherulites in the polymer P, e.g. PP, nylon, PBT, which is intrinsically semicrystalline, thereby leading to a micromesh-like structure, where V is excluded from the crystal phases and concentrated within the interlamellar spaces.

[0118] For applications involving frequent contact with water flow, the polymer P or the carrier C is preferably a rigid substrate and even displays shear thickening behaviour so that it does not deform easily while actively stiffens at high shear rate. With a rigid backing, the foulantsubstrate interface, where the composition V resides, is exerted by a much larger portion of the hydrodynamic force. This concentrated force acts to break adhesive forces that hold the foulants rather than being dissipated into elastic deformation of the substrate, leading to a more effective cleaning effect.

[0119] To enhance long-term resistance to microbial or fungal attack at static condition, the composition V preferably contains a relatively higher proportion of ether bonds, e.g., alkyl polyol ethers, compared to other hydrolysable linkages commonly present in its structure, such as amide, urethane, ester, and carbonate bonds in ascending order of susceptibility to enzymatic degradation by hydrolases. On the other hand, the hydrocarbon component of composition V may allow for a moderate degree of unsaturation, featuring 1 to 3 double (> C=C<) bonds (preferably in cis- rather than trans- configurations) or triple (-C=C-) bonds at intermediate carbon positions in the structure. For example, a cis double bond is thought to possess a rigid bend or kink which distorts the tight packing of lipid bilayer molecules afterME_962110409_1being intercalated into a cell membrane at the point of interaction. It may help disrupt the structural integrity and fluidity of the cell membrane, leading to increased permeability, leakage of cellular contents, and eventually cell death. Unsaturation increases susceptibility to abiotic oxidative degradation, which may subsequently facilitate oxidoreductase activity. A suitable trade-off is thus recommended by controlling the number of double or triple carbon-carbon bonds within the composition V. With the inception of the chemical structures of several commercial cell lysis and virus inactivation detergents, such as Triton™ X-100, Genapol® x-080, Ecosurf™ EH-9, Deviron® 13-S9 and Tergitol™ 15-S-9, the composition V may prefer to introduce sterically crowded substituents in a geminal or vicinal carbon position along a hydrocarbon chain, e.g. methyl, ethyl, propyl, butyl, phenyl, cyclohexyl, isophorone, biphenyl, naphthalene, norbornane, adamantane or comprise a free or reacted alcohol group (-OH or -O-) affixed to a secondary carbon atom along a hydrocarbon chain to augment its spatial bulkiness.Process for preparing a composition

[0120] In a second aspect there is provided a process for preparing a composition comprising:• combining a substrate, a linker or precursor thereto comprising a hydrophobic moiety and a functional molecule comprising a semi-hydrophobic or hydrophilic group and a hydroxyl, amino or thiol group, to form a blend, and• melt processing the blend

[0121] In another aspect there is provided a composition prepared by the process of the second aspect.

[0122] The substrate, linker or precursor thereto and functional molecule may be as described above in in respect of the composition of the first aspect.

[0123] In general, the process involves mixing the substrate, linker or precursor thereto and functional molecule at elevated temperature using a melt processing method. That is, the substrate, linker or precursor thereto and functional molecule are all provided as separate components and combined in a single step. Without wishing to be bound by theory, it is believed that when mixed at elevated temperature, and in some embodiments in the presence of a radical initiator, the substrate, linker or precursor thereto and functional molecule react with one another to form a composition as described herein. Various possibilities as to howME_962110409_1the substrate, linker or precursor thereto and functional molecule may react and attach to one another are described above with respect to the composition. Alternatively, the substrate, linker or precursor thereto and functional molecule may react and attach to one another in a manner not described herein. Alternatively, the substrate, linker or precursor thereto and / or functional molecule may not attach to one another and merely form a mixture.

[0124] The substrate may be a polymer, such as a polyester, a polyamide, a polyolefin, or a polysiloxane. The polyester may be polybutylene terephthalate (PBT), optionally wherein the PBT is modified with glycol. The polyamide may be nylon 6, nylon 12, nylon 6,6 or a mixture thereof. The polysiloxane may be poly(dimethylsiloxane). The polyolefin may be polyethylene, polypropylene, or copolymers thereof or with other monomers, for example with vinyl acetate (forming polyethylene vinyl acetate). The substrate may be an inorganic material such as calcium carbonate, silica, alumina, titania or boron nitride. The substrate may be calcium carbonate or boron nitride.

[0125] In the case of a process of the second aspect, the linker may be a precursor to a linker as described in respect of the composition of the first aspect. The linker precursor may be a Michael acceptor, such as an a,p-unsaturated carboxylic acid or acid anhydride. The linker precursor may be selected from maleic anhydride, maleic acid, fumaric acid, and itaconic acid. The linker precursor may be a cyclic alkylcarbonate, such as propylene carbonate, ethylene carbonate, and vinylene carbonate. The linker precursor may be propylene carbonate or ethylene carbonate. The linker precursor may be a polysilazane, such as perhydropolysilazane, or a polysiloxane.

[0126] The functional molecule may be a molecule comprising the functional moiety as described in respect of the composition of the first aspect, that is, it is understood that the functional moiety of the first aspect is derived from a functional molecule. The functional molecule may be a molecule comprising one or more ethylene glycol groups. The molecule comprising one or more ethylene glycol groups may be poly(ethylene glycol) (PEG), an amine, such as an alkylamine, a C8-C20 alkyl alcohol, acid or amide derivative thereof, a triglyceride, such as the triester of glycerol and ricinoleic acid, sorbitan or a C8-C20 alkyl acid ester thereof, or a siloxane or polysiloxane. The functional molecule may be a molecule comprising one or more amine or amine oxide groups. The functional molecule comprising one or more amine or amine oxide groups may be a C8-C20 alkyl acid or amide derivative thereof, a siloxane or polysiloxane.ME_962110409_1

[0127] In some embodiments, a first composition is prepared according to the process of the second aspect. This may be referred to as a masterbatch. The first composition may then be combined with a second polymer and subject to a second step of melt processing. The second polymer may be a polyolefin as described above, a co-polymer of styrene, such as styrene-ethylene-butylene-styrene, or a polysiloxane such as poly(dimethylsiloxane).

[0128] The process of the second aspect may comprise combining the substrate with more than one linker precursor and / or more than one functional molecule.

[0129] The process of the second aspect may further comprise combining the substrate, the linker or precursor thereto and the functional molecule with a free radical initiator such as an organic peroxide, such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane or dicumyl peroxide.

[0130] In one embodiment, there is provided a process of the second aspect wherein the substrate is a polyester, the linker precursor is an a,p-unsaturated carboxylic acid or acid anhydride and the functional molecule is a molecule comprising one or more ethylene glycol groups.

[0131] In one embodiment, there is provided a process of the second aspect wherein the substrate is a polyester or a polyamide, the linker precursor is cyclic alkylcarbonate and the functional molecule is a molecule comprising one or more amine or amine oxide groups.Efficacy

[0132] The compounds of the present invention may resist fungal growth on the surface. They may give resistance to bacterial adherence to the surface. These may be measured by ASTM E3371-22 (bacterial repellency) orASTM G21-15 (fungal resistance). The compositions of the invention and / or composites comprising a polymer combined with the compositions of the invention, may exhibit nil fungal growth i.e. 0 ratings under ASTM G21-15 and / or bacterial repellency of at least 10%, or at least about 20, 30, 40, 50, 60, 70, 80, 90, 95, 96, 97, 98, 99, 99.5, 99.9, 99.95 or 99.9% as measured by ASTM E3371-22.Examples

[0133] The present disclosure is further described below by reference to the following nonlimiting examples.ME_962110409_1Table 1. Preliminary screening of V by measuring the non-adherence of bacteria under ASTM E3371-22 against the pristine (unmodified) polymer (P) and its persistence to fungal growth under ASTM G21-15, which were carried out by an accredited testing laboratory.Test compounds (V) Polymer (P) Processing % resistance to phr = parts per hundred by weight method bacterial adherence under ASTM E3371-22 and / or rating of fungal growth under ASTM G21- 15Example 1 PBT-A (94.1 phr) Method 1* 99.99% S. A. ** 0.5 phr MAH + 5 phr PEG + 0.4 phr 97.6% E. Coli ** AOAPBT-B (94.1 phr) Method 1* 99.9% S. A. ** [W = -CH=CH- on MAH (L); Y = 99.8% E. Coli ** PEG]AAO is a stabilizer additiveExample 2 PBT-B (94.1 phr) Method 1* 99.99% S. A. ** 0.5 phr ITA + 5 phr PEG + 0.4 phrAOA[W = -CH2-C(=CH2)- on ITA (L); Y= PEG]AAO is a stabilizer additiveExample 3 PBT-A (89.5 phr) Method 1* 93.3% S. A. ** 5 phr FA + 2 phr OrganoSi + 0.5phr OA18E2 + 0.5 phr AC1810 +0.5 phr AC1815 + 0.5 phr AC1860+ 0.5 phr AC1201 + 0.5 phrAC1205 + 0.5 phrAC1210[W = -CH=CH- on FA (L); X =OrganoSi, OA18E2, AC1810,AC1815, AC1860, AC1201,AC1205 or AC1210]ME_962110409_1Example 4 PBT-A (90 phr) Method 1* 93.7% S. A. ** 5 phr FA + 2 phr OrganoSi + 3 phrAC1210[W = -CH=CH- on FA (L); X =OrganoSi or AC1210]Example 5 PBT-A (94.5 phr) Method 1* 99.56% S. A. ** 0.5 phr ITA + 5 phr CO-40 99.15% E. Coli ** [W = -CH2-C(=CH2)- on ITA (L); X = CO-40; Y = polyoxyethylene on CO-40] PBT-B (94.5 phr) Method 1* 99.999% S. A. **= CO-40; Y = polyoxyethylene onCO-40]Example 6 PBT-A (94.5 phr) Method 1* 99.56% S. A. ** 0.5 phr ITA + 5 phr EL-40 99.89% E. Coli ** [W = -CH2-C(=CH2)- on ITA (L); X _PBT-B (94.5 phr) Method 1* 99.99% S. A. ** = EL-40; Y = polyoxyethylene onEL-40]Example 7 PBT-B (94.5 phr) Method 1* 99.99% S. A. ** 0.5 phr ITA + 5 phr ED3060[W = -CH2-C(=CH2)- on ITA (L); Y= ED3060]Example 8 PBT-B (94 phr) Method 1* 99.999% S. A. ** 0.5 phr ITA + 5 phr HCO[W = -CH2-C(=CH2)- on ITA (L); X= HCO]Example 9 PETG (94 phr) Method 1* 79.1% S. A. ** 1 phr ITA + 5 phr HCO[W = -CH2-C(=CH2)- on ITA (L); X PA612 (94 phr) Method 1* 97.65% S. A. ** = HCO]Example 10 PA612 (93.6 phr) Method 1* 17.33% S. A. ** 1 phr PC + 0.2 phr MIPA + 0.1 phrDEI PA + 0.1 phr Tl PA + 5 phr HCO[W = -CH2-CHCH3- on MIPA,DEI PA, TIPA or PC (L); X = HCO]ME_962110409_1Example 11 PBT-B (94.8 phr) Method 1* 99.999% S. A. ** 0.2 phr DEIPA + 5 phr TO[W = -CH2-CHCH3- on DEIPA (L);X = TO]Example 12 PETG (99 phr) Method 1* 46.75% S. A. ** 0.5 phr PC + 0.3 phr CAO + 0.2 phrCDEA PA612 (99 phr) Method 1* 94.95% S. A. ** [W = -CH2-CHCH3- on PC (L); X =CAO or CDEA] PA12 (99 phr) Method 1* 95% S. A. **All 0 ratings (Days: 7 / 14 / 21 / 28) Example 13 PETG (99 phr) Method 1* 54.23% S. A. ** 0.5 phr PC + 0.5 phr CAO[W = -CH2-CHCH3- on PC (L); X =CAO]Example 14 PETG (93.5 phr) Method 1* 14.44% S. A. ** 1 phr ITA + 5 phr HEL + 0.5 phrOFX-A[W = -CH2-C(=CH2)- on ITA (L); X= HEL or OFX-A; Y =polyoxyethylene on HEL]Example 15 PA12 (96 phr) Method 1* 98.6% S. A. ** 2.5 phr PC + 1.5 phr CAO[W = -CH2-CHCH3- on PC (L); X =CAO]Example 16 PA12 (95 phr) Method 1* 99.999% S. A. ** 2.5 phr PC + 1.5 phr CAO + 1 phrCDEA[W = -CH2-CHCH3- on PC (L); X =CAO or CDEA]ME_962110409_1Example 17 PA612 (91 phr) Method 1* 99.999% S. A. ** 2 phr C10-DA + 2 phr CL + 5 phrGLY[W = -(CH2)8- on C10-DA (L) or - (CH2)5- on CL (L); X = GLY; Y =polyoxyethylene on GLY]Example 18 PA612 (94 phr) Method 1* 99.34% S. A. ** 1 phr PC + 5 phr APG[W = -CH2-CHCH3- on PC (L); X =APG; Y = polyglucoside on APG]Example 191ststep: extrusion of MB (EVA) as a V- Modified P (see Figure 3)MB (EVA): 92 phr EVA (Pi) + 2 phr AA / MA + 1 phrPVA Method 1*+ 0.5 phr DCP* + 1 phr AEG + 1 phr MO + 1 phr CD +1 phr HCO + 0.5 phr RBW[V from W = MO, CD or RBW; W-Y = AEO; X = HCO;Y = AA / MA or PVA]* DCP is a thermal initiator2ndstep: extrusion of the second polymer P2with MB (EVA) followed by injection molding 1.5 phr MB (EVA) PA12 (P2) (98.5 Method 297.1% S. A. ** phr) All 0 ratings (Days: 7 / 14 / 21 / 28) Example 201ststep: extrusion of MB(PPO) & MB(PPR) as V-Modified P (see Figure 3)MB (PPO): 67.34 phr PPR (Pi) + 28.86 phr PPO (Pi) Method 1*+ 3 phr MAH + 0.8 phr DCPAMB (PPR): 95.5 phr PPR (Pi) + 2 phr MAH + 0.5 phr Method 1*DCPA+2 phr St[V from (W-X)m-W, where W = non-grafted polyolefin(PPO / PPR) segment; X = MAH-grafted polyolefin(PPO / PPR) segment]ADCP is a thermal initiatorME_962110409_12ndstep: extrusion of the second polymer P2 with MB(PPO) and MB(PPR) followed by injection molding20 phr MB (PPO) + 20 phr MB PA6-A (P2) (60 Method 2 17.1% S. A. ** (PPR) phr)PA6-B (P2) (60 Method 2 45.5% S. A. ** Phr)Example 211ststep: extrusion of MB-C & MB-C(AF) as V-Modified C (see Figure 4)MB-C: 40 g SPT + 10 g PEG-DS + 25 g AEO + 30 mL distilled water (mixing with a spatula and 900W microwave oven treatment for 5 minutes) and subsequently, melt-compounding with 100 g PPR (Pv) by extrusionMB-C(AF): 40 g SPT + 10 g PEG-DS + 30 mL distilled water (mixing with a spatula and 900W microwave oven treatment for 5 minutes) and subsequently, melt-compounding with 100 g PPR (Pv) by extrusion[C = SPT; Pv= PPR; V from W = fatty acid coated inherently on the surfaces of CaCO3particles (SPT); W-Y-W= PEG-DS; W-Y = AEO]2ndstep: Dry blending of the second polymer P2with MB-C followed by injection molding 10 phr M B-C PPR (P2) (90 phr) Method 3 57.1 % S. A. **TPE (P2) (90 phr) Method 3 99.999% S. A. **or: Extrusion of the second polymer P2with MB-C vs. MB-C(AF) followed by injection molding10 phr MB-C TPE (P2) (90 phr) Method s 99.999% S. A. **10 phr MB-C(AF) TPE (P2) (90 phr) Method s 79.8% S. A. **Example 22 PDMS (98.3 phr) Method 1#99.99% S. A. ## 0.2 phr PHPS + 0.5 phr OFX-B + 1phr DBPH-AA[W = Si-N-Si on PHPS (L); X =OFX-B; Y = PEG on OFX-B]ADBPH-A is a curing agentME_962110409_1Example 23 PDMS (97.6 phr) Method 1#99.9% SA.** 0.4 phr PHPS + 1 phr OFX-B + 1phr DBPH-AA[W = Si-N-Si on PHPS (L); X =OFX-B; Y = PEG on OFX-B]ADBPH-A is a curing agentExample 24 PDMS (98.28 Method 1#99.99% SA.** 0.02 phr ITA + 0.2 phr PMX + 0.5 Phr)phr OFX-B + acetone (5 mL per500 g PDMS) + 1 phr DBPH-AA[W = -CH2-C(=CH2)- on ITA (L) orSi-O-Si on PMX (L); X = OFX-B; Y= PEG on OFX-B]ADBPH-A is a curing agentExample 25 PDMS (97.4 phr) Method 1#99.99% SA.** 0.2 phr ITA + 0.4 phr PMX + 1 phrOFX-B + acetone (5 mL per 500 gPDMS) + 1 phr DBPH-AA[W = -CH2-C(=CH2)- on ITA (L) orSi-O-Si on PMX (L); X = OFX-B; Y= PEG on OFX-B]ADBPH-A is a curing agentExample 26 PDMS (98.62 Method 1#99.999% SA.** 0.1 phr ITA + 0.04 phr PMX + 0.04 phr)phr PHPS + 0.2 phr OFX-B +acetone (15 mL per 500 g PDMS)+ 1 phr DBPH-AA[W = -CH2-C(=CH2)- on ITA (L) orSi-O-Si on PMX (L) or Si-N-Si onPHPS (L); X = OFX-B; Y = PEG onOFX-B]ADBPH-A is a curing agentME_962110409_1Example 271ststep: preparation of BN-1, BN-2 & BN-3 as V-Modified C by ultrasonic homogenization (see Figure 5)BN-1:Addition and ultrasonic homogenization sequence(i) + 7 g BN + 140 mL isopropanol, followed by 15-minute homogenization(ii) + 7 mL MIPA, followed by 3-minute homogenization(iii) + 7 mL EP-EtO-Si, followed by 3-minute homogenization(iv) + 1.4 mL TW20 + 1.4 mL TW80 + 1.4 mL TWIN, followed by 3-minute homogenization[C = BN; W = -CH2-CHCH3- on MIPA (L); X = EP-EtO-Si, TW20, TW80 and TWIN; Y = PEG on EP-EtO-Si, TW20, TW80 and TWIN]BN-2:Addition and ultrasonic homogenization sequence(i) + 7 g BN + 140 mL isopropanol, followed by 15-minute homogenization(ii) + 7 mL D230, followed by 3-minute homogenization(iii) + 7 mL EP-EtO-Si, followed by 3-minute homogenization(iv) + 3 mL BE561, followed by 3-minute homogenization[C = BN; W = -[CH(CH3)-CH2-O]2.5-CH2- CH(CH3)- on D230 (L); X = EP-EtO-Si and BE561; Y = PEG on EP-EtO-Si and BE561]BN-3:Addition and ultrasonic homogenization sequence(i) + 5.5 g BN + 110 mL isopropanol, followed by 10-minute homogenization(ii) + 2 mL PHPS, followed by 2-minute homogenization(iii) + 5 mL EP-EtO-Si, followed by 2-minute homogenization(iv) + 2 mL LHS, followed by 2-minute homogenization[C = BN; W = Si-N-Si on PHPS (L); X = EP-EtO-Si and LHS; Y = PEG on EP-EtO-Si] 2ndstep: kneading of the second polymer P2 with BN-1, BN-2 or BN-3 and subsequently with 1.2 phr DBPH-B' followed by compression moldingSi-BN-1 PDMS (P2) Method 3§99.5% S. A. **1.5 kg All 0 ratings(Days: 7 / 14 / 21 / 28)ME_962110409_1Si-BN-2 99.8% S. A. **0 / 0 / 0 / 1 ratings (Days: 7 / 14 / 21 / 28) Si-BN-3 99.0% S. A. **0 / 1 / 2 / 4 ratings (Days: 7 / 14 / 21 / 28)ADBPH-B is a curing agent

[0134] * Method 1*. The resinous sample was produced by extrusion (melt compounding) of the test composition V and the polymer P together in one pass on a co-rotating twin-screw extruder employing a processing temperature window of 180-230°C for producing PBT, PETG, PA6, PA612 and PA12 while 160-180°C for producing TPE, PPR, PPO and EVA, followed subsequently by pelletization of the melt extrudate.

[0135] Method 2 is used in Examples 19 and 20. Thus Method 1 was used initially to provide a combination of Pi with W and X and / or Y so as to produce a V-modified Pi. This was then used as a masterbatch to blend with a second polymer P2 by melt processing to produce a final resin. The resulting melt processed blend was then injection molded to generate the final product. In Example 19, this final resin is MB(EVA) / PA12 and in Example 20 two separate resins are produced: (MB(PPO) / MB(PPR)) / PA6-A and (MB(PPO) / MB(PPR)) / PA6-B. In Example 20, two separate masterbatches MB(PPO) and MB(PPR) were prepared individually and then combined together with PA6-A or PA6-B.

[0136] Method 3 is used in Example 21. Thus desired components of V together with C were combined in water and then subjected to microwave treatment. The resulting mixture (V-modified C) was then melt compounded with polymer Pvto produce a masterbatch. This masterbatch was then combined with a second polymer P2 either by dry blending or melt compounding to form an end formulation which was then injection molded to generate the final product.

[0137] These experiments illustrate that the adhesion of bacteria may be affected by the nature of the second polymer as well as by the presence of additives, e.g. fatty alcohol polyoxyethylene ether, in the masterbatch (in particular in the treatment of C).ME_962110409_1

[0138] ** Test specimen of a flat 60-mm circular plate with a thickness of 1.5 mm and a smooth surface was produced with a single-screw injection molding machine for conduct of performance testing under ASTM E3371-22 or ASTM G21-15. For ASTM E3371-22, the unmodified polymer substrate served as the control to determine the % resistance to bacterial adherence of the modified sample, which was derived from the same base polymer. The mould culture used for ASTM G21-15 fungus resistance testing over an entire 28-day incubation period: Aspergillus brasiliensis (ATCC 9642), Penicillium pinophilum (ATCC 11797), Chaetomium globosum (ATCC 6205), Gliocladium virens (ATCC 9645) and Aureobasidium pullulans (ATCC 15233). The rating scale of 0 to 4 represents the degree of fungal growth observed on the surface of a test specimen i.e. 0 = None (no growth on specimen surface); 1 = Traces of growth (less than 10%); 2 = Light growth (10-30%); 3 = Medium growth (31-60%); and 4 = Heavy growth (61% to complete coverage).

[0139] #Method 1#. The raw materials of the composition V were weighed (per 500 g PDMS) and then mixed in a polypropylene conical flask on a magnetic stirrer for about 5 minutes at a speed setting of 3CO-400 rpm. The resulting viscous liquid mixture or particulate slurry (due to the presence of ITA powders) was further diluted with acetone to reduce its viscosity for the ease of processing (no dilution was conducted in Examples 22 and 23) and stirred for another 5 minutes. After being kept in the dark for about 24 hours at ambient temperature, the composition V was added slowly onto a gum paste of PDMS substrate over a two-roll mill and kneaded for about 15 rolling cycles at room temperature, followed by 15 more cycles of kneading along with addition of DBPH as the curing agent, ensuring that all ingredients were dispersed into the PDMS matrix. The whole blending process took about 20-25 minutes. Acetone evaporated quickly upon addition during the process. The unmodified control was prepared in a similar manner by two-roll milling without adding the composition V but rather only DBPH. Both unmodified and modified samples of PDMS, prepared as flat putty sheets, were left at ambient temperature for 24 hours before proceeding to compression molding.

[0140] These experiments illustrate that a suitable combination of W and X is required, and a higher amount of OFX-B (X), that intrinsically shows hydrophilic polyethylene glycol content, in the case of a heat-cured silicone rubber does not necessarily warrant a higher repellency of the polymer substrate towards bacteria.

[0141] §Method 3§. Hexagonal boron nitride powder flakes were dispersed in isopropanol (5% w / v) using an ultrasonic homogenizer (machine model: UW-050; power: 500W; frequency: 20 kHz; probe: 8-mm diameter titanium alloy) in a 250 mL beaker sealed withME_962110409_1aluminium foil. The temperature was maintained between 50 and 55°C during the dispersing process. The raw materials for composition V were sequentially added using a pipette, followed by 2-3 minutes of homogenization to produce three distinct V-modified C particle dispersion samples (milky): BN-1, BN-2, and BN-3 (optionally, the modified boron nitride particles may be separated from isopropanol by vacuum microfiltration or centrifugation and re-suspended in fresh isopropanol by sonication before use). After cooling to ambient temperature, 15 mL of each dispersion sample was subsequently transferred into a 25-mL polypropylene conical flask and rendered thrice, hence resulting in a total volume of 45 mL being collected for each sample. The collected samples in isopropanol were again kept in the dark at ambient temperature for approximately 12 hours. Then two-roll milling was performed on a larger production scale this time against a gum paste of PDMS (1.5 kg) being considered as the second polymer P2. The kneading process involved about 20 rolling cycles at room temperature for each dispersion sample (shaken before use), followed by an additional 20 cycles with the use of DBPH of a different supplier as the curing agent, ensuring uniform dispersion of all ingredients within the PDMS matrix. The entire compounding process took approximately 30-45 minutes. The unmodified control sample was prepared similarly through two-roll milling, but without adding the V-modified C composition, using only DBPH. Both the unmodified and modified PDMS samples, obtained as gum-like rolls, were allowed to stay at ambient temperature for at least 24 hours before undergoing compression molding.

[0142] In Example 27, the amine group on a bi- or poly-functional molecule W (such as MIPA, D230, or PHPS) chemisorbs preferentially onto the boron atoms of the boron nitride particles as the anchor. This leaves a second functional group (either an amine or hydroxyl) available to react with the epoxy group of a PEG-containing functional molecule X (EP-EtO-Si), followed by reactions between the hydroxyl groups of another X molecule (such as TW20, BE561, or LHS) and the epoxy groups of EP-EtO-Si. The surface-modified boron nitride particles i.e. V-modified C are then dispersed within a PDMS prepolymer matrix as a second polymer substrate and crosslinked as a single entity via thermal free radical curing using DBPH, consistent with the procedures in Examples 22-26.

[0143] The post-cured, unmodified PDMS sample maintained a rating of 1 at all tested time points (7, 14, 21, and 28 days) in tests against a co-culture of fungi under ASTM G21-15 (conducted in a medium without readily available carbon food source), suggesting that some proprietary additives from the PDMS supplier or contaminants unavoidably introduced during the compounding / molding process may be metabolizable by fungi. Post-cured PDMS samples modified with BN-1, BN-2, or BN-3 (namely, Si-BN-1, Si-BN-2 or Si-BN-3) overall exhibitedME_962110409_1good bacterial repellency, irrespective of the raw materials selected for composition V, compared to the unmodified PDMS sample. They may differentiate among themselves according to the charges borne by V with this order of performance: Si-BN-2 (cationic) > Si-BN-1 (non-ionic) > Si-BN-3 (zwitterionic). Specifically, they all achieved a rating of 0, indicating initial protection against fungal attachment for at least one week, whereas the unmodified sample already showed a rating of 1 at this stage. However, such protection diminished over longer culture durations under static conditions. These experiments suggest that introducing a relatively higher proportion of ether bonds, as compared to the charges borne, in composition V (e.g., Si-BN-1 with relatively more PEG content, followed by Si-BN-2 containing polypropylene glycol) would ensure long-term resistance to fungal attack. The Si-BN-1 specimens and the unmodified PDMS ones were additionally subjected to Soxhlet extraction against petroleum ether at a temperature of 65±5°C for a duration of 6 hours in accordance with the ASTM G 120- 15 standard, which is more aggressive than the standard food contact migration tests mandated by Regulation (EU) No 10 / 2011, FDA or LFGB that are adopted by most consumer products to demonstrate safety. This extraction procedure was carried out by an accredited laboratory. The percentage of soluble residues (both nonvolatile and semivolatile) was measured to be 2.36% for Si-BN-1 and 2.09% for the unmodified sample on a weight basis which were likely due to uncrosslinked siloxane oligomers, decomposition byproducts and contaminants. The low residual content, and such a similarity in the residual content between the two suggests that V is strongly bonded to the substrate C and the robust binding of the V-modified C composition within the PDMS matrix.

[0144] ^Test specimen of a flat 50 mm x 50 mm square plate (or 150 mm x 150 mm square plate for the production scale at 1.5 kg PDMS) with a thickness of 2 mm was produced by compression molding of a putty sample of PDMS for bacterial adherence testing under ASTM E3371-22. The molding temperature and cycle time for preparing the test specimens were set at 185°C and 80 seconds respectively.

[0145] The impact of adding various types of extra additives (0.5% by weight) was also examined, including polymethylsilsesquioxane (Tospearl® 120A), Green® HK-165 (supplier: Dongguan Hongcheng), Honeywell AClyn® 285P, and microcrystalline cellulose (PH 101; supplier: Shaanxi Zhengyi) into PBT-B of Example 5 for the purpose of minimizing the mold shrinkage after injection molding, comparing it to the pristine PBT-B control. All treated samples demonstrated the ability to sustain at least 99% resistance of adherence toward S. A. when compared to the control under ASTM E3371-22.ME_962110409_1

[0146] In relation to the manner in which the substrate, linker and functional molecule reactwith one another, the inventors postulate as follows in relation to examples involving an acid containing linker and PEG-containing or polyol(e.g. castor oil)-containing functional molecule(e.g. Examples 1-9). There is a kinetic preference for PEG / polyol to react with maleic anhydride (MAH), forming a PEG / polyol-maleic acid (MA) monoester adduct, primarily because the reactive end-groups of PBT are dilute and sterically shielded within a high-viscosity polymer matrix. In the polyester melt, the carboxylic acid group attributed to MA, one terminus of the monoester adduct, that is generated from ring-opening of MAH is significantlymore reactive than a neutral hydroxyl group (the other terminus of the adduct). This acid group functions as an autocatalyst, facilitating faster incorporation into PBT via acidolysis or esterification than could be achieved by PEG-OH or polyol-OH alone. Consequently, the small molecular footprint of W, say MAH, is critical; it rapidly functionalizes PEG into a more aggressive reactant, whereas if a sterically bulkier molecule is selected for W, it will suffer froma reduced diffusion rate and lower reactive site accessibility. For the latter, side product, suchas PBT-PEG-W, other than the desired PBT-W-PEG may appear.*** Abbreviations:AA / MA: Poly(Acrylic Acid-co-Maleic Acid) (supplier: Qingdao Fumaisi)AC1201: Lauryl Amine Ethoxylate (supplier: Linyi Lvsen)AC1205: PEG-5 Laurylamine (supplier: Linyi Lvsen)AC1210: PEG-10 Laurylamine (supplier: Linyi Lvsen)AC1810: PEG-10 Stearamine (supplier: Linyi Lvsen)AC1815: PEG-15 Stearamine (supplier: Linyi Lvsen)AC1860: PEG-60 Stearamine (supplier: Linyi Lvsen)AEO: Fatty Alcohol Polyoxyethylene Ether (5) (supplier: Linyi Lvsen)AO: Irganox® 1010 Antioxidant StabilizerAPG: APG1214 (C12-14 Alkyl Glucoside) (supplier: Linyi Lvsen)BE561: Nouryon Berol® 561 (Quaternary Ammonium Compounds, Coco Alkylbis(hydroxyethyl)methyl, Ethoxylated, Chlorides)BN: Hexagonal Boron Nitride (particle size: 1 μm) (supplier: Shanghai Muheng)C10-DA: 1,10-Decanedicarboxylic AcidCAO: CAQ-30 Cocamidopropylamine Oxide (30%) (supplier: Linyi Lvsen)CDEA: CDEA 6501 Cocamide Diethanolamine 1:1 (containing glycerol) (supplier: Linyi Lvsen)CL: CaprolactamCO-40: Cremophor® CO-40 (PEG-40 Hydrogenated Castor Oil)ME_962110409_1CD: Camphor Oil Distillate (supplier: Hangzhou Jimu Crafts)D230: Polyetheramine D230 (supplier: Linyi Lvsen)DCP: Dicumyl PeroxideDEIPA: Diethanol IsopropanolamineDBPH-A: C-15 (2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 42%) (supplier: Shenzhen Kanglibang) DBPH-B: C-15C (2,5-dimethyl-2,5-di(tert-butylperoxy)hexane) (supplier: Zhongshan Hongnuo New Material)E. Coli: Escherichia coli (ATCC 8739)ED3060: Genapol® ED 3060 (Ethylenediamine tetrakis(ethoxylate-b-propoxylate))EL-40: PEG-40 Castor Oil (supplier: Linyi Lvsen)EP-EtO-Si: Epoxy Polyether Silicone Oil Xt-12K (supplier: Dongguan Xiangtao)EVA: Evathene® UE630 (Ethylene-Vinyl Acetate Copolymer)FA: Fumaric AcidGLY: Glycerox® 767 (PEG-6 Caprylic / Capric Triglycerides)HCO: Hydrogenated Castor Oil (Flakes)HEL: HEL-40 PEG-40 Hydrogenated Castor Oil (supplier: Jiangsu Haian Petrochemical Plant) ITA: Itaconic AcidLHS: Lauryl Hydroxysultaine LHS-45 (45%) (supplier: Linyi Lysen)MAH: Maleic AnhydrideMIPA: MonoisopropanolamineMO: CYQY 038 Mustard Oil (supplier: Wuxi Chuanye)OrganoSi: Trisiloxane Ethoxylate (supplier: Qingdao Runhebao)OA18E2: Oleyl Amine Polyoxyethylene Ether (2) (supplier: Linyi Lvsen)OFX-A: Xiameter® OFX-8040A (Di-amino Functional Siloxane Polymer)- OFX-B: Xiameter® OFX-0193 (PEG-12 Dimethicone)- PA6-A: Sunylon® Nylon 6 Chip NP2800- PA6-B: Libolon® Nylon 6 Chip N 150-300- PA612: Grilon® XE 3938 polyamidePA12: Vestamid® L 1600 polyamide 12PBT-A: Ultradur® B 2550 polybutylene terephthalatePBT-B: Toraycon™ 1401 X06 polybutylene terephthalatePC: Propylene CarbonatePDMS: Shin-Etsu CHN-6500-U General Purpose Silicone Rubber (HCR)PEG: Polyethylene Glycol 8000, NF GradePEG-DS: Hallstar® PEG 400 DS (Polyethylene Glycol Distearate)PETG: Skygreen® S2008 (Glycol-modified Polyethylene Terephthalate)ME_962110409_1PHPS: Mingyi Silicone MY-PHPS (Perhydropolysilazane, 20% solid content in butyl ether)PMX: Xiameter® PMX-0156 (Polydimethylsiloxane Polymer with Reactive Silanol Functionality) PPO: Vistamaxx™ 6202 (Isotactic Propylene-co-ethylene Elastomer)PPR: Clyrell RC5056 (Polypropylene-co-ethylene Random Copolymer)PVA: PVA 1788 (Polyvinyl Alcohol) (supplier: Tianjin Fangdatongzheng)RBW: Rice Bran Wax (supplier: Huzhou Shengtao)S. A.: Staphylococcus aureus (ATCC 6538P)SPT: Winnofil® SPT PCC (Ultrafine, Surface treated Precipitated Calcium Carbonate).St: StyreneTIPA: TriisopropanolamineTPE: Gallonprene® GP210-7010 (Styrene-Ethylene-Butylene-Styrene (SEBS) Thermoplastic Elastomer) TO: Ripe Tung Oil (supplier: Dabie Mountain Tung Oil Workshop)TW20: Tween® 20TW80: Tween® 80- TWIN: TEGO® Twin 4100

[0147] For instance, V may comprise L and Y, as in Examples 1 and 2, or may comprise L and X, like Examples 3 and 4.

[0148] In Examples 1 and 2, both gradient and alternating spatial arrangements, as illustrated in Scheme 1, are possible. Thus, V may have a gradient structure of W - Y or W - Y - W, or may have an alternating structure of W - Y - W - Y -... - W i.e. (W-Y)m-W. The latter structure may be polydispersed with respect to chain length if Y (e.g. PEG) has two hydroxyl end groups and polymerizes further with MAH or ITA (the covalent linker L), which also bears two carboxylate groups. This reaction can occur via condensation reactions in tandem, yielding short alkyl groups as spacer units (W): -CH=CH- in the case of MAH or -CH2-C(=CH2)- in the case of ITA while forming ester bonds in between. AO may be added into the formulation with the aim to minimize the thermal decomposition of PEG (Y) during melt compounding.Moreover, the covalently bonded MAH or ITA unit may further undergo oxa-Michael addition reaction between the hydroxyl group on Y (PEG) and the a,p-unsaturated carbonyl unit on theMAH or ITA, resulting in branching with similar structure. It is thought that the terminal Y (e.g.PEG) is replaced with a carboxylate group containing an a,p-unsaturated carbonyl unit (Z) instead of a hydroxyl unit if the chain end is MAH or ITA instead of PEG owing to the fact that a higher molar ratio of W to Y is used. In Example 12, where CAO is used as X however, the composition of V may end up a specific headgroup of methylamine oxide (Z) which is structurally analogous to a typical osmolyte molecule of trimethylamine N-oxide.ME_962110409_1

[0149] In Examples 5 and 6, the component Y stems from a tertiary structure of PEG and is possibly produced by intermolecular coupling of two PEG units given on the X (castor oil triglyceride) compounds in the case of using CO-40 or EL-40 via ITA (L) serving as a covalent molecular bridge with ester linkages, followed by oxa-Michael addition of another PEG from X to ITA resulting in an ether linkage. The effect of hydrogenation of the castor oil by comparing the antibiofouling performance between Example 5 and Example 6 is insignificant.

[0150] Examples 8 and 9 do not include any PEG-based compounds, where PEG or adducts of ethylene oxide is a common hydrophilic macromolecular crowder known for its antibiofouling properties. The screening test results suggest that the use of a hydrophilic substance in the formulation is not a prerequisite for achieving the antibiofouling behavior of the modified base polymer product. Besides, no specific bioactives or biocidal additives are employed. One can mimic Examples 8 and 9 by using a maleated PPO / PPR, which is slightly hydrophilic as the test composition V (like in Example 20) rather than the combination of HCO and ITA to chemically modify the base polymer. The idea works although the performance may not be as promising.

[0151] Those skilled in the art will appreciate that the disclosure described herein is susceptible to variations and modifications other than those specifically described. It is to be understood that the disclosure includes all such variations and modifications. The disclosure also includes all of the steps, features, compositions and compounds referred to or indicated in this specification, individually or collectively, and any and all combinations of an two or more of said steps, features, compositions and compounds.ME_962110409_1

Claims

Claims:

1. A composition comprising:• a substrate;• a linker attached to the substrate, said linker comprising a hydrophobic moiety; and• a functional moiety comprising a semi-hydrophobic group and / or a hydrophilic group;wherein the functional moiety is coupled to the linker and comprises a hydroxyl, amino or thiol group or a derivative thereof.

2. The composition of claim 1 wherein the linker is attached covalently to the substrate.

3. The composition of claim 1 or claim 2 wherein the substrate is a polymer.

4. The composition of any one of claims 1 to 3 wherein the substrate is a polymer comprising an ester or amide linkage.

5. The composition of any one of claims 1 to 4 wherein the substrate is a polyester or a polyamide.

6. The composition of any one of claims 1 to 5 wherein the substrate comprises an inorganic substance.

7. The composition of any one of claims 1 to 6 wherein the substrate comprises a surface treated calcium carbonate.

8. The composition of claim 7 wherein the surface treated calcium carbonate is a fatty acid coated calcium carbonate.

9. The composition of any one of claims 1 to 8 wherein the substrate is particulate.

10. The composition of any one of claims 1 to 9 wherein the composition is dispersed within a polymeric matrix.

11. The composition of any one of claims 1 to 10 wherein the linker comprises a hydrocarbon chain.ME_962110409_112. The composition of 11 wherein the hydrocarbon chain is C2 or C3.

13. The composition of any one of claims 1 to 12 wherein the linker is, or is derived from, a bis-carboxylic acid or a cyclic carbonate or a cyclic anhydride or a lactam or a bisamide or a cyclic imide.

14. The composition of any one of claims 1 to 13 wherein the functional moiety is covalently coupled to the linker.

15. The composition of any one of claims 1 to 14 wherein the functional moiety comprises an ether linkage.

16. The composition of any one of claims 1 to 15 wherein the functional moiety comprises a polyether chain.

17. The composition of any one of claims 1 to 16 wherein the functional moiety comprises a polyoxyethylene group.

18. The composition of any one of claims 1 to 17 wherein the functional moiety has a functional headgroup attached to the hydroxyl, amino or thiol group, whereby the functional headgroup attached to said hydroxyl, amino or thiol group is the derivative thereof.

19. The composition of claim 18 wherein the functional headgroup is capable of one or more of:• improving biocompatibility and / or haemocompatibility of the composition;• enhancing affinity of the composition to water molecules;• reducing protein unfolding;• enhancing lubricity of the composition;• enhancing resistance of the composition to oxidation;• enabling site-specific recognition and / or bioconjugation and / or immobilisation of biomolecules on the composition;• enabling branching and / or crosslinking of the composition.ME_962110409_120. A process for preparing a composition comprising:• combininga substrate,a linker or precursor thereto comprising a hydrophobic moiety anda functional molecule comprising a semi-hydrophobic or hydrophilic group and a hydroxyl, amino or thiol group,to form a blend, and• melt processing the blend.

21. The process of claim 20 wherein the substrate comprises a polymer.

22. The process of claim 20 or claim 21 wherein the substrate comprises an ester or an amide linkage.

23. The process of any one of claims 20 to 22 wherein the linker or precursor thereto comprises a cyclic carbonate or an α,β-unsaturated carbonyl compound.

24. The process of any one of claims 20 to 23 wherein the linker or precursor thereto is selected from the group consisting of an optionally substituted ethylene carbonate an α,β-unsaturated carboxylic acid, an α,β-unsaturated ester, an α,β-unsaturated anhydride, an α,β-unsaturated amide and an α,β-unsaturated lactam, wherein optional substituents on ethylene carbonate are selected from C1 to C6 straight chain, branched and cyclic alkanes.

25. The process of any one of claims 20 to 24 wherein the melt processing is conducted at a temperature of between about 150 and about 250°C.

26. The process of any one of claims 20 to 25 comprising attaching a functional headgroup to the hydroxyl, amino or thiol group.

27. The process of any one of claims 20 to 26 additionally comprising combining the composition with a polymer.ME_962110409_128. The process of claim 27 wherein combining the composition with a polymer comprises melt processing.ME_962110409_1

Images