Functionalised crosslinker

Abstract

The invention relates to a polymer for treating a surface, which polymer comprises n reactive intermediate precursor groups, wherein n is an integer equal to or greater than 3; and m groups for controlling surface-initiated reversible-deactivation radical polymerization (SIRDRP), wherein m is an integer equal to or greater than 3. The groups for controlling SIRDRP are selected from groups which comprise an initiator and groups which comprise a chain transfer agent (CTA). The reactive intermediate precursor groups are selected from carbene precursor groups and nitrene precursor groups. The carbene precursor groups are selected from hydrazone groups of formula (A), diazo groups of formula (B) and diazirine groups of formula (C), and the nitrene precursor groups are azide groups of formula (D): wherein R1 is H or –S(O)2R2, and R2 is an unsubstituted or substituted C1-6 alkyl group or an unsubstituted or substituted aryl group. The invention also relates to a process for producing a treated substrate, which treated substrate has a surface suitable for SIRDRP. The invention also relates to a treated substrate having a surface suitable for SIRDRP, and to treated substrates obtainable by the aforementioned process of the invention. The invention also relates to a treated substrate which comprises: a substrate, a reacted polymer disposed on a surface of the substrate, and a further polymer, grown by SIRDRP, bonded to the reacted polymer.

Description

[0001] FUNCTIONALISED CROSSLINKER

[0002] FIELD OF THE INVENTION

[0003] The invention relates to a polymer suitable for treating a surface. The polymer may be used to treat a surface of a substrate in order to render the surface suitable for carrying out surface -initiated reversible-deactivation radical polymerization (SIRDRP). The invention also relates to a treated substrate, which treated substrate has a surface suitable for SIRDRP, and to a process for producing such a treated substrate. The invention also relates to such treated substrates which comprise a further polymer, grown thereon by SIRDRP.

[0004] BACKGROUND TO THE INVENTION

[0005] Modifying the surfaces of materials with polymers is significant to many fields. To address the limitations of physiosorbed coatings (such as weak adhesion, sensitivity to environmental conditions, and limited long-term stability), covalently surface-tethered polymers provide a robust alternative.

[0006] Surface initiated reversible-deactivation radical polymerization (SIRDRP) is a technique that allows growth of polymers from surfaces with control over molecular weight and polydispersity. This control is essential when grafting on porous materials, such as membranes, or particles as it prevents unwanted blocking of the pore structure due to uncontrolled polymer growth.

[0007] For SIRDRP either an initiator or chain transfer agent (CTA) needs to be present on the surface. These chemical species can be added using surface treatment / surface modification. On materials with active surfaces, such as silica, ceramics, cellulose, etc., this is easily achieved but on more inert engineering polymers, such as PP, PE, Nylons, PES, PVDF, etc., this requires more forcing methods.

[0008] Several methods have been reported such as (1) plasma assisted grafting followed by chemical coupling to incorporate an initiator or CTA, or (2) using a small molecule carbene precursor containing a pendant coupled initiator (Z. Hu et al., Materials Letters 218, 2018, 157-160).

[0009] While both methods work at a lab scale they are not suited to commercial manufacture as they are inefficient with reactions involving harsh chemicals needing to be carried out on the membrane for extended periods, require extensive washing with harsh solvents to remove dimerised or ungrafted material (which means they are environmentally poor, costly, and if not done efficiently lead to leachable / extractables and, in the case of small molecule carbenes, introduce linking chemistry which is weak and prone to attack in use over time). Other systems are limited and specific to materials with functional surfaces such as metals or glass (silanes, thiols etc.).

[0010] SUMMARY OF THE INVENTION

[0011] The present invention relates to a manufacturing-friendly and robust method for introducing either an initiator or CTA functionality to a surface using a surface treatment polymer comprisingmultiple (for instance at least 3, or at least 4, and preferably at least 5 or more) reactive intermediate precursor groups (e.g. carbene precursor groups or nitrene precursor groups) per molecule, and also multiple (generally at least 3) initiator or CTA functionalities per molecule. Having multiple reactive intermediate precursor groups allows curing and crosslinking in 3 dimensions, which results in a long-range crosslinked network being formed post curing. These long-range networks reduce the probability of having ungrafted material, such as dimerised molecules and side products, etc., in the surface coating, which is major disadvantage of a small molecule approach. This in turn means that there is less of a requirement to wash the surface thoroughly to remove loose material after modification, which reduces the need for using harsh organic solvents, making the process both more cost effective and environmentally friendly. The high cross-link density also advantageously imparts stability in both water and organic solvents, and typically also in harsher conditions such as strong acid or base. The highly reactive carbene and nitrene groups of the polymer, when generated, form strong covalent attachments to the surface of the substrate, including even to the surfaces of inert materials, meaning that a wide variety of surfaces can be rendered suitable for carrying out surface -initiated reversible-deactivation radical polymerization (SIRDRP), using a polymer of the invention.

[0012] Accordingly, the invention provides a polymer for treating a surface, which polymer comprises: n reactive intermediate precursor groups, wherein n is an integer equal to or greater than 3; and m groups for controlling surface-initiated reversible -deactivation radical polymerization (SIRDRP), wherein m is an integer equal to or greater than 3, wherein: the groups for controlling SIRDRP are selected from groups which comprise an initiator and groups which comprise a chain transfer agent (CTA); and the reactive intermediate precursor groups are selected from carbene precursor groups and nitrene precursor groups, wherein the carbene precursor groups are selected from hydrazone groups of formula (A), diazo groups of formula (B) and diazirine groups of formula (C), and the nitrene precursor groups are azide groups of formula (D):

[0013]

[0014] wherein R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-6 alkyl group or an unsubstituted or substituted aryl group.

[0015] The invention also provides a process for producing a treated substrate, which treated substrate has a surface suitable for surface-initiated reversible -deactivation radical polymerization (SIRDRP), which process comprises:

[0016] (a) contacting a surface of a substrate with a polymer for treating a surface, wherein the polymer for treating a surface comprises: n reactive intermediate precursor groups, wherein n is an integer equal to or greater than 3; and m groups for controlling SIRDRP, wherein m is an integerequal to or greater than 3, wherein: the groups for controlling SIRDRP are selected from groups which comprise an initiator and groups which comprise a chain transfer agent (CTA); and the reactive intermediate precursor groups are selected from carbene precursor groups and nitrene precursor groups, wherein the carbene precursor groups are selected from hydrazone groups of formula (A), diazo groups of formula (B) and diazirine groups of formula (C), and the nitrene precursor groups are azide groups of formula (D):

[0017] wherein

[0018]

[0019] n unsubstituted or substituted aryl group; and

[0020] (b) generating carbene or nitrene reactive intermediate groups from the reactive intermediate precursor groups, so that the carbene or nitrene reactive intermediate groups react with the surface of the substrate.

[0021] The invention also provides a treated substrate which is obtainable by a process of the invention as defined above.

[0022] The process of the invention may further comprise (c) exposing the surface suitable for surface -initiated reversible-deactivation radical polymerization (SIRDRP) to one or more monomers, and polymerising the one or monomers on the surface by SIRDRP.

[0023] The invention also provides a treated substrate having a surface suitable for surface-initiated reversible-deactivation radical polymerization (SIRDRP), wherein the treated substrate comprises: (a) a substrate; and (b) a reacted polymer disposed on a surface of the substrate, wherein the reacted polymer is obtainable by generating carbene or nitrene reactive intermediate groups from reactive intermediate precursor groups of a polymer for treating a surface, so that the carbene or nitrene reactive intermediate groups react with said surface of the substrate, wherein the polymer for treating a surface comprises n of said reactive intermediate precursor groups, wherein n is an integer equal to or greater than 3, and m groups for controlling SIRDRP, wherein m is an integer equal to or greater than 3, wherein: the groups for controlling SIRDRP are selected from groups which comprise an initiator and groups which comprise a chain transfer agent (CTA); and the reactive intermediate precursor groups are selected from carbene precursor groups and nitrene precursor groups, wherein the carbene precursor groups are selected from hydrazone groups of formula (A), diazo groups of formula (B) and diazirine groups of formula (C), and the nitrene precursor groups are azide groups of formula (D):

[0024]

[0025] wherein R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-e alkyl group or an unsubstituted or substituted aryl group.

[0026] The invention also provides a treated substrate which comprises: (a) a substrate; (b) a reacted polymer disposed on a surface of the substrate; and (c) a further polymer, grown by surface-initiated reversible-deactivation radical polymerization (SIRDRP), bonded to the reacted polymer (b), wherein the reacted polymer is obtainable by generating carbene or nitrene reactive intermediate groups from reactive intermediate precursor groups of a polymer for treating a surface, so that the carbene or nitrene reactive intermediate groups react with said surface of the substrate, wherein the polymer for treating a surface comprises n of said reactive intermediate precursor groups, wherein n is an integer equal to or greater than 3, and m groups for controlling SIRDRP, wherein m is an integer equal to or greater than 3, wherein:

[0027] the groups for controlling SIRDRP are selected from groups which comprise an initiator and groups which comprise a chain transfer agent (CTA); and

[0028] the reactive intermediate precursor groups are selected from carbene precursor groups and nitrene precursor groups, wherein the carbene precursor groups are selected from hydrazone groups of formula (A), diazo groups of formula (B) and diazirine groups of formula (C), and the nitrene precursor groups are azide groups of formula (D):

[0029]

[0030] wherein R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-6 alkyl group or an unsubstituted or substituted aryl group,

[0031] and wherein the further polymer, grown by SIRDRP, is obtainable by exposing the reacted polymer (b) to one or more monomers, and polymerising the one or monomers by surface -initiated reversible-deactivation radical polymerization.

[0032] DETAILED DESCRIPTION OF THE INVENTION

[0033] Chemical definitions

[0034] As used herein, a C1-20 alkyl group is an unsubstituted or substituted, straight or branched chain saturated hydrocarbon radical having from 1 to 20 carbon atoms. Typically it is CMO alkyl, forexample methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, or Ci-6 alkyl, for example methyl, ethyl, propyl, butyl, pentyl or hexyl, or C1-4 alkyl, for example methyl, ethyl, i-propyl, n-propyl, t-butyl, s-butyl or n-butyl. In one embodiment, it is a C2-20 alkyl group or, for instance, a C3-20 alkyl or a C4-20 alkyl group. When an alkyl group is substituted it typically bears one or more (e.g. one, two, three or four) substituents selected from substituted or unsubstituted C1-20 alkyl; substituted or unsubstituted C2-20 alkenyl; substituted or unsubstituted C2-20 alkynyl; substituted or unsubstituted aryl; substituted or unsubstituted aralkyl; halo; cyano; keto; amino; C O alkylamino; di(Ci-io)alkylamino; arylamino; diarylamino; arylalkylamino; amido; acylamido; C1-20 haloalkyl (e.g. -CF3); ester; acyl; acyloxy; CMO alkoxy; aryloxy; nitro; hydroxyl, carboxy; sulfonic acid; sulfonyl; sulphonamide; sulfhydryl (i.e. thiol, -SH); CMO alkylthio; arylthio; tri(Ci-2o alkyl)silyl; aryldi(Ci-2o alkyl)silyl; diaryl(Ci-2o alkyl)silyl; and triarylsilyl.

[0035] Examples of substituted alkyl groups include C1-20 haloalkyl, alkoxyalkyl and alkaryl groups. The term alkaryl, as used herein, pertains to a C1-20 alkyl group in which at least one hydrogen atom (e.g., 1, 2, 3) has been replaced with an aryl group. Examples of such groups include, but are not limited to, benzyl (phenylmethyl, PI1CH2-), benzhydryl (PI12CH-), trityl (triphenylmethyl, PI13C-), phenethyl (phenylethyl, PI1-CH2CH2-), styryl (Ph-CH=CH-), cinnamyl (Ph-CH=CH-CH2-).

[0036] Typically a substituted C1-20 alkyl group carries 1, 2 or 3 substituents, for instance 1 or 2. A C1-20 haloalkyl group is a straight or branched chain saturated C1-20 alkyl group in which at least one hydrogen atom has been replaced with a halogen atom, typically F, Cl or Br. In a Cnhaloalkyl group, where n is from 1 to 20, the number of hydrogen atoms replaced with a halogen atom may be from n to (2n+l). The halogen atoms may be the same or different. C1-20 haloalkyl groups include C1-20 fluoroalkyl groups and C1-20 perfluoroalkyl groups, as defined below. A C1-20 haloalkyl group may have at least two halogen atoms or, for instance, at least three halogen atoms.

[0037] A C1-20 fluoroalkyl group is a straight or branched chain saturated C1-20 alkyl group in which at least one hydrogen atom has been replaced with a fluorine atom. In a Cnfluoroalkyl group, where n is from 1 to 20, the number of hydrogen atoms replaced with a fluorine atom may be from n to (2n+l). Thus, C1-20 fluoroalkyl groups include C1-20 perfluoroalkyl groups, in which all the hydrogen atoms that would otherwise have been present are replaced with a fluorine atom. Typically, a C 1.20 fluoroalkyl group has at least two fluorine atoms, more typically at least three fluorine atoms.

[0038] Typically a C1-20 fluoroalkyl group is a C2-20 fluoroalkyl group, or for instance a C3-20 fluoroalkyl group. Typically, a C2-20 fluoroalkyl group has at least three fluorine atoms, more typically at least four fluorine atoms. Typically, a C3-20 fluoroalkyl group has at least three fluorine atoms, more typically at least four fluorine atoms or, for instance, at least six fluorine atoms.

[0039] A C1-20 perfluoroalkyl group is a straight or branched chain saturated perfluorinated hydrocarbon radical having from 1 to 20 carbon atoms. “Perfluorinated” in this context means completely fluorinated such that there are no carbon-bonded hydrogen atoms replaceable with fluorine. Typically it is C1-12 perfluoroalkyl, for example trifluoromethyl (Ci), pentafluoroethyl (C2),perfluoropropyl (C3) (including pcrfluoro-w-propyl and pcrfluoro- / .so-propyl). perfluorobutyl (C4) (including pcrfluoro-w-but l. perfluoro -iso -butyl, pcrfluoro-scc-butyl and perfluoro-tert-butyl), perfluoropentyl (C5), perfluorohexyl (Ce), perfluoroheptyl (C7), perfluorooctyl (Cs), perfluorononyl (C>), perfluorodecyl (C10), perfluoroundecyl (Cn) and perfluorododecyl (C12), including straight chained and branched isomers thereof.

[0040] A C1-20 hydrocarbon moiety is a straight-chained or branched, saturated or unsaturated hydrocarbon moiety having from 1 to 20 carbon atoms. A C1-20 hydrocarbon moiety may be unsubstituted or substituted, the substituents, unless otherwise specified, being selected from those listed above for C1-20 alkyl groups. Typically, when a C1-20 hydrocarbon moiety is substituted, it is substituted by from one to four (e.g. one, two, three or four) substituents.

[0041] A tri(Ci-2o alkyl)silyl group represents a group of formula: -Si(R )(R”)(R”’) wherein R’, R” and R’”, which are the same or different, are unsubstituted or substituted, straight or branched chain C1-20 alkyl groups as defined above.

[0042] A aryldi(Ci-2o alkyl)silyl group represents a group of formula: -Si(R )(R”)(R”’) wherein R’ and R”, which are the same or different, are unsubstituted or substituted, straight or branched chain C1-20 alkyl groups as defined above, and wherein R’” is an unsubstituted or substituted aryl group.

[0043] A diaryl(Ci-2o alkyl)silyl group represents a group of formula: -Si(R )(R”)(R”’) wherein R’ is an unsubstituted or substituted, straight or branched chain C1-20 alkyl group as defined above, and wherein R” and R’”, which are the same or different, are unsubstituted or substituted aryl groups.

[0044] A triarylsilyl group represents a group of formula: -Si(R )(R”)(R”’) wherein R’, R” and R’”, which are the same or different, are unsubstituted or substituted aryl groups.

[0045] A C2-20 alkenyl group is a straight or branched group, which contains from 2 to 20 carbon atoms. One or more double bonds may be present in the alkenyl group, typically one double bond. A C2-20 alkenyl group is typically ethenyl or a C3-10 alkenyl group, i.e. a C2-10 alkenyl group, more typically a C2-6 alkenyl group. A C3-10 alkenyl group is typically a C3-6 alkenyl group, for example allyl, propenyl, butenyl, pentenyl or hexenyl. A C2-4 alkenyl group is ethenyl, propenyl or butenyl. An alkenyl group may be unsubstituted or substituted by one to four (e.g. one, two, three or four) substituents, the substituents, unless otherwise specified, being selected from those listed above for C1-20 alkyl groups. Where two or more substituents are present, these may be the same or different.

[0046] A C2-20 alkynyl group is a straight or branched group which, unless otherwise specified, contains from 2 to 20 carbon atoms. One or more triple bonds, and optionally one or more double bonds may be present in the alkynyl group, typically one triple bond. A C2-20 alkynyl group is typically ethynyl or a C3-10 alkynyl group, i.e. a C2-10 alkynyl group, more typically a C2-6 alkynyl group. A C3-10 alkynyl group is typically a C3-6 alkynyl group, for example propynyl, butynyl, pentynyl or hexynyl. A C2-4 alkynyl group is ethynyl, propynyl or butynyl. An alkynyl group may be unsubstituted or substituted by one to four substituents (e.g. one, two, three or four), the substituents,unless otherwise specified, being selected from those listed above for C1-20 alkyl groups. Where two or more substituents are present, these may be the same or different.

[0047] An aryl ring is an unsubstituted or substituted aromatic ring of covalently linked carbon atoms. Typically, the aryl ring is a 5 - or 6- membered aryl ring, examples of which include cyclopentadienyl (Cp) and phenyl. An aryl ring may be unsubstituted or substituted by, typically, one to five substituents (e.g. one, two, three, four or five), the substituents, unless otherwise specified, being selected from those listed above for C1-20 alkyl groups. Where two or more substituents are present, these may be the same or different.

[0048] A heteroaryl ring is an unsubstituted or substituted heteroaromatic ring of covalently linked atoms including one or more heteroatoms. The one or more heteroatoms are typically selected from nitrogen, phosphorus, silicon, oxygen and sulfur (more commonly from nitrogen, oxygen and sulfur). A heteroaryl ring is typically a 5- or 6- membered heteroaryl ring containing at least one heteroatom selected from nitrogen, phosphorus, silicon, oxygen and sulfur (more commonly selected from nitrogen, oxygen and sulfur). It may contain, for example, 1, 2 or 3 heteroatoms. Examples of heteroaryl rings include pyridine, pyrazine, pyrimidine, pyridazine, furan, thiofuran, pyrazole, pyrrole, oxazole, oxadiazole, isoxazole, thiadiazole, thiazole, isothiazole, imidazole and pyrazole. A heteroaryl ring may be unsubstituted or substituted by, typically, one to four substituents (e.g. one, two, three or four), the substituents, unless otherwise specified, being selected from those listed above for C1-20 alkyl groups. Where two or more substituents are present, these may be the same or different.

[0049] A C5-10 carbocyclic ring is an unsubstituted or substituted closed ring of from 5 to 10 covalently linked carbon atoms, which ring is saturated or unsaturated. Typically, the C5-10 carbocyclic ring is not an aromatic ring. Typically the C5-10 carbocyclic ring is a C5-6 carbocyclic ring. The carbocyclic ring may be saturated or unsaturated. Thus, the term C5-10 carbocyclic ring includes the sub-classes C5-10 cycloalkyl ring, C5-10 cycloalkyenyl ring and C5-10 cycloalkynyl ring. When a C5-10 carbocyclic ring is substituted it typically bears one or more substituents selected from those listed above for C1-20 alkyl groups. Examples of C5-10 carbocyclic rings include, but are not limited to:

[0050] cyclopentane (C5), cyclohexane (Ce), cycloheptane (C7), methylcyclopropane (C4), dimethylcyclopropane (C5), methylcyclobutane (C5), dimethylcyclobutane (Ce), methylcyclopentane (Ce), dimethylcyclopentane (C7), methylcyclohexane (C7), dimethylcyclohexane (Cs), menthane (C10), cyclopentene (C5), cyclopentadiene (C5), cyclohexene (Ce), cyclohexadiene (Ce), methylcyclopropene (C4), dimethylcyclopropene (C5), methylcyclobutene (C5), dimethylcyclobutene (Ce), methylcyclopentene (Ce), dimethylcyclopentene (C7), methylcyclohexene (C7), dimethylcyclohexene (Cs).

[0051] A C5-10 heterocyclic ring is an unsubstituted or substituted closed ring of from 5 to 10 covalently linked atoms, which ring is saturated or unsaturated, wherein at least one of the ring atoms is a multivalent ring heteroatom, for example, nitrogen, phosphorus, silicon, oxygen, or sulfur (though more commonly nitrogen, oxygen, or sulfur). Typically, the C5-10 heterocyclic ring is not an aromaticring. Typically, the C5-10 heterocyclic ring has from 1 to 4 heteroatoms, the remainder of the ring atoms are carbon. Typically, the C5-10 heterocyclic ring is a C5-6 heterocyclic ring in which from 1 to 4 of the ring atoms are ring heteroatoms, and the remainder of the ring atoms are carbon atoms. In this context, the prefixes C5-10 and C5-6 denote the number of ring atoms, or range of number of ring atoms. When a C5-10 heterocyclic ring is substituted it typically bears one or more substituents selected from those listed above for C1-20 alkyl groups.

[0052] Examples of monocyclic C5-10 heterocyclic rings include, but are not limited to:

[0053] Ni: pyrrolidine (tetrahydropyrrole) (C5), pyrroline (e.g., 3-pyrroline, 2,5 -dihydropyrrole) (C5), 2H-pyrrole or 3H-pyrrole (isopyrrole, isoazole) (C5), piperidine (Ce), dihydropyridine (Ce), tetrahydropyridine (Ce), azepine (C7);

[0054] Oi : oxolane (tetrahydrofuran) (C5), oxole (dihydrofuran) (C5), oxane (tetrahydropyran) (Ce), dihydropyran (Ce), pyran (Ce), oxepin (C7);

[0055] Si: thiolane (tetrahydrothiophene) (C5), thiane (tetrahydrothiopyran) (Ce), thiepane (C7); O2: dioxolane (C5), dioxane (Ce), and dioxepane (C7);

[0056] O3: trioxane (Ce);

[0057] N2: imidazolidine (C5), pyrazolidine (diazolidine) (C5), imidazoline (C5), pyrazoline (dihydropyrazole) (C5), piperazine (Ce);

[0058] N1O1: tetrahydrooxazole (C5), dihydrooxazole (C5), tetrahydroisoxazole (C5), dihydroisoxazole (C5), morpholine (Ce), tetrahydrooxazine (Ce), dihydrooxazine (Ce), oxazine (Ce);

[0059] N1S1: thiazoline (C5), thiazolidine (C5), thiomorpholine (Ce);

[0060] N2O1: oxadiazine (Ce);

[0061] Oi Si: oxathiole (C5) and oxathiane (thioxane) (Ce); and,

[0062] N1O1S1: oxathiazine (Ce).

[0063] A C3-20 carbocyclyl group is an unsubstituted or substituted monovalent moiety obtained by removing a hydrogen atom from an alicyclic ring atom of a carbocyclic ring of a carbocyclic compound, which moiety has from 3 to 20 carbon atoms (unless otherwise specified), including from 3 to 20 ring atoms. The carbocyclyl ring may be saturated or unsaturated. Thus, the term "carbocyclyl" includes the sub-classes cycloalkyl, cycloalkyenyl and cycloalkynyl. Preferably, each ring has from 5 to 7 ring atoms. Examples of groups of C3-20 carbocyclyl groups include C3-10 carbocyclyl, C5-7 carbocyclyl and C5-6 carbocyclyl. When a C3-20 carbocyclyl group is substituted it typically bears one or more substituents (typically one, two, three or four substituents) selected from those listed above for C1-20 alkyl groups.

[0064] Examples of C3-20 carbocyclyl groups include, but are not limited to, those derived from saturated monocyclic hydrocarbon compounds:

[0065] cyclopropane (C3), cyclobutane (C4), cyclopentane (C5), cyclohexane (Ce), cycloheptane (C7), methylcyclopropane (C4), dimethylcyclopropane (C5), methylcyclobutane (C5),dimethylcyclobutane (Ce), methylcyclopentane (Ce), dimethylcyclopentane (C7), methylcyclohexane (C7), dimethylcyclohexane (Cs), menthane (C10);

[0066] unsaturated monocyclic hydrocarbon compounds:

[0067] cyclopropene (C3), cyclobutene (C4), cyclopentene (C5), cyclopentadiene (C5), cyclohexene (Ce), cyclohexadiene (Ce), methylcyclopropene (C4), dimethylcyclopropene (C5), methylcyclobutene (C5), dimethylcyclobutene (Ce), methylcyclopentene (Ce), dimethylcyclopentene (C7), methylcyclohexene (C7), dimethylcyclohexene (Cs);

[0068] saturated polycyclic hydrocarbon compounds:

[0069] thujane (C10), carane (C10), pinane (C10), bomane (C10), norcarane (C7), norpinane (C7), norbomane (C7), adamantane (Cw), decalin (decahydronaphthalene) (C10); unsaturated polycyclic hydrocarbon compounds: camphene (C10), limonene (C10), pinene (C10);

[0070] polycyclic hydrocarbon compounds having an aromatic ring:

[0071] indene (C>), indane (e.g., 2,3 -dihydro- IH-indene) (C>), tetraline

[0072] (1,2,3,4-tetrahydronaphthalene) (C10), acenaphthene (C12), fluorene (C13), phenalene (C13), 5, 5,8,8-tetramethyl tetraline (C14), acephenanthrene (C15), aceanthrene (Cie), cholanthrene (C20).

[0073] Further examples of C3-20 carbocyclyl groups include C3-20 halocarbocyclyl groups, C3-20 fluorocarbocyclyl groups, C3-20 perfluorocarbocyclyl groups and C3-10 cycloalkyl groups.

[0074] A C3-20 halocarbocyclyl group is a C3-20 carbocyclyl group in which at least one hydrogen atom has been replaced with a halogen atom, typically F, Cl or Br. The halogen atoms may be the same or different. C3-20 halocarbocyclyl groups include C3-20 fluorocarbocyclyl groups and C3-20 perfluorocarbocyclyl groups, as defined below. A C3-20 halocarbocyclyl group may have at least two halogen atoms or, for instance, at least three or at least four, at least five or at least six halogen atoms.

[0075] A C3-20 fluorocarbocyclyl group is a C3-20 carbocyclyl group in which at least one hydrogen atom has been replaced with a fluorine atom. C3-20 fluorocarbocyclyl groups include C3-20 perfluorocarbocyclyl groups, as defined below. A C3-20 fluorocarbocyclyl group may have at least two fluorine atoms or, for instance, at least three or at least four, at least five or at least six fluorine atoms.

[0076] A C3-20 perfluorocarbocyclyl group a perfluorinated C3-20 carbocyclyl group. “Perfluorinated” in this context means completely fluorinated such that there are no carbon-bonded hydrogen atoms replaceable with fluorine.

[0077] A C3-10 cycloalkyl group or moiety is a 3 - to 10- membered unsubstituted or substituted group or moiety, typically a 3 -to 6-membered group or moiety, which may be a monocyclic ring or which may consist of two or more fused rings. Examples of C3-10 cycloalkyl groups or moieties include cyclopropane (C3), cyclobutane (C4), cyclopentane (C5), cyclohexane (Ce), cycloheptane (C7), methylcyclopropane (C4), dimethylcyclopropane (C5), methylcyclobutane (C5), dimethylcyclobutane (Ce), methylcyclopentane (Ce), dimethylcyclopentane (C7), methylcyclohexane (C7), dimethylcyclohexane (Cs), menthane (C10), thujane (C10), carane (C10),pinane (Cio), bomane (Cio), norcarane (C7), norpinane (C7), norbomane (C7), adamantane (Cio) and decalin (decahydronaphthalene) (Cio).

[0078] A C3-20 heterocyclyl group is an unsubstituted or substituted monovalent, monocyclic, bicyclic or tricyclic moiety obtained by removing a hydrogen atom from a ring atom of a heterocyclic compound, which moiety has from 3 to 20 ring atoms (unless otherwise specified), of which from 1 to 10 are ring heteroatoms. Preferably, each ring has from 3 to 7 ring atoms, of which from 1 to 4 are ring heteroatoms. When a C3-20 heterocyclyl group is substituted it typically bears one or more substituents selected from those listed above for C1-20 alkyl groups. Typically a substituted C3-20 heterocyclyl group carries 1, 2 or 3 substituents, for instance 1 or 2.

[0079] Examples of groups of heterocyclyl groups include C3-20 heterocyclyl, C5-20 heterocyclyl, C3-15 heterocyclyl, C5-15 heterocyclyl, C3-12 heterocyclyl, C5-12 heterocyclyl, C3-10 heterocyclyl, C5-10 heterocyclyl, C3-7 heterocyclyl, C5-7 heterocyclyl, and C5-6 heterocyclyl.

[0080] Examples of monocyclic C3-20 heterocyclyl groups include, but are not limited to, those derived from:

[0081] Ni: aziridine (C3), azetidine (C4), pyrrolidine (tetrahydropyrrole) (C5), pyrroline (e.g., 3-pyrroline, 2,5-dihydropyrrole) (C5), 2H-pyrrole or 3H-pyrrole (isopyrrole, isoazole) (C5), piperidine (Ce), dihydropyridine (Ce), tetrahydropyridine (Ce), azepine (C7);

[0082] Oi : oxirane (C3), oxetane (C4), oxolane (tetrahydrofuran) (C5), oxole (dihydrofuran) (C5), oxane (tetrahydropyran) (Ce), dihydropyran (Ce), pyran (Ce), oxepin (C7);

[0083] Si: thiirane (C3), thietane (C4), thiolane (tetrahydrothiophene) (C5), thiane (tetrahydrothiopyran) (Ce), thiepane (C7);

[0084] O2: dioxolane (C5), dioxane (Ce), and dioxepane (C7);

[0085] O3: trioxane (Ce);

[0086] N2: imidazolidine (C5), pyrazolidine (diazolidine) (C5), imidazoline (C5), pyrazoline (dihydropyrazole) (C5), piperazine (Ce);

[0087] N1O1: tetrahydrooxazole (C5), dihydrooxazole (C5), tetrahydroisoxazole (C5), dihydroisoxazole (C5), morpholine (Ce), tetrahydrooxazine (Ce), dihydrooxazine (Ce), oxazine (Ce);

[0088] N1S1: thiazoline (C5), thiazolidine (C5), thiomorpholine (Ce);

[0089] N2O1: oxadiazine (Ce);

[0090] Oi Si: oxathiole (C5) and oxathiane (thioxane) (Ce); and,

[0091] N1O1S1: oxathiazine (Ce).

[0092] Examples of C3-20 heterocyclyl groups which are also aryl groups are described below as heteroaryl groups.

[0093] An aryl group is a substituted or unsubstituted, monocyclic or bicyclic aromatic group which typically contains from 6 to 14 carbon atoms, preferably from 6 to 10 carbon atoms in the ring portion. Examples include phenyl, naphthyl, indenyl and indanyl groups. An aryl group is unsubstituted or substituted. When an aryl group as defined above is substituted it typically bears oneor more substituents (for instance, one, two, three, four or five substituents) selected from those listed above for C1-20 alkyl groups. A substituted aryl group may be substituted in two positions with a single unsubstituted or substituted C1-6 alkylene group, or with a bidentate group represented by the formula -X-C1-6 alkylene, or -X-C1-6 alkylene-X-, wherein X is selected from O, S and NR, and wherein R is H, aryl or C1-6 alkyl. Thus a substituted aryl group may be an aryl group fused with a cycloalkyl group or with a heterocyclyl group. A further example of a substituted aryl group is a Ce-io perfluoroaryl group.

[0094] A Ce-io perfluoroaryl group is a perfluorinated aryl group which contains from 6 to 10 carbon atoms in the ring portion. “Perfluorinated” in this context means completely fluorinated such that there are no carbon-bonded hydrogen atoms replaceable with fluorine. Typically it is pentafluorophenyl .

[0095] The term aralkyl as used herein, pertains to an aryl group in which at least one hydrogen atom (e.g., 1, 2, 3) has been substituted with a C1-20 alkyl group. Examples of such groups include, but are not limited to, tolyl (from toluene), xylyl (from xylene), mesityl (from mesitylene), and cumenyl (or cumyl, from cumene), and duryl (from durene).

[0096] The ring atoms of an aryl group may include one or more heteroatoms, as in a heteroaryl group. Such an aryl group (a heteroaryl group) is a substituted or unsubstituted mono- or bicyclic heteroaromatic group which typically contains from 6 to 10 atoms in the ring portion including one or more heteroatoms. It is generally a 5 - or 6-membered ring, or two fused rings each of which is the same or different and typically independently selected from a 5 -membered ring and a 6-membered ring, containing at least one heteroatom selected from O, S, N, P, Se and Si. It may contain, for example, 1, 2 or 3 heteroatoms. Examples of heteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, furanyl, thienyl, pyrazolidinyl, pyrrolyl, oxazolyl, oxadiazolyl, isoxazolyl, thiadiazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, quinolyl and isoquinolyl. A heteroaryl group may be unsubstituted or substituted, for instance, as specified above for aryl. Typically it carries 0, 1, 2 or 3 substituents.

[0097] A C1-20 alkylene group is an unsubstituted or substituted bidentate moiety obtained by removing two hydrogen atoms, either both from the same carbon atom, or one from each of two different carbon atoms, of a hydrocarbon compound having from 1 to 20 carbon atoms (unless otherwise specified), which may be aliphatic or alicyclic, and which may be saturated, partially unsaturated, or fully unsaturated. Thus, the term "alkylene" includes the sub-classes alkenylene (C1-20 alkenylene), alkynylene (C1-20 alkynylene), cycloalkylene, etc. Typically it is C1-10 alkylene, or C1-6 alkylene. Typically it is C1-4 alkylene, for example methylene, ethylene, i-propylene, n-propylene, t-butylene, s-butylene or n-butylene. It may also be pentylene, hexylene, heptylene, octylene and the various branched chain isomers thereof. An alkylene group may be unsubstituted or substituted, for instance, as specified above for alkyl. Typically a substituted alkylene group carries 1, 2 or 3 substituents, for instance 1 or 2.In this context, the prefixes (e.g., C1-4, C1-7, C1-10, C2-7, C3-7, etc.) denote the number of carbon atoms, or range of number of carbon atoms. For example, the term "Ci.4alkylene," as used herein, pertains to an alkylene group having from 1 to 4 carbon atoms. Examples of groups of alkylene groups include C1-4 alkylene ("lower alkylene"), C1-7 alkylene and Ci- 10 alkylene.

[0098] Examples of linear saturated C1-7 alkylene groups include, but are not limited to, -(CH2)n-where n is an integer from 1 to 7, for example, -CH2- (methylene), -CH2CH2-(ethylene), -CH2CH2CH2- (propylene), and -CH2CH2CH2CH2- (butylene).

[0099] Examples of branched saturated C1-7 alkylene groups include, but are not limited

[0100] to, -CH(CH3)-, -CH(CH3)CH2-, -CH(CH3)CH2CH2-, -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2-, -C H2CH(CH3)CH2CH2-, -CH(CH2CH3)-, -CH(CH2CH3)CH2-, and -CH2CH(CH2CH3)CH2-.

[0101] Examples of linear partially unsaturated C1-7 alkylene groups include, but is not limited to, -CH=CH- (vinylene), -CH=CH-CH2-, -CH2- CH=CH2-, -CH=CH-CH2-CH2-, -CH=CH-CH2-CH2-CH2-, -CH=CH-CH=CH-, -CH=CH-CH=CH-CH2-, -CH=CH-CH=CH-CH2-CH2-, -CH=CH-CH2-CH=CH-, and -CH=CH-CH2-CH2-CH=CH-.

[0102] Examples of branched partially unsaturated C1-7 alkylene groups include, but is not limited to, -C(CH3)=CH-, -C(CH3)=CH-CH2-, and -CH=CH-CH(CH3)-.

[0103] Examples of alicyclic saturated C1-7 alkylene groups include, but are not limited to, cyclopentylene (e.g., cyclopent-1, 3-ylene), and cyclohexylene (e.g., cyclohex- 1,4-ylene).

[0104] Examples of alicyclic partially unsaturated C1-7 alkylene groups include, but are not limited to, cyclopentenylene (e.g., 4-cyclopenten-l, 3-ylene), cyclohexenylene (e.g., 2-cyclohexen-l,4-ylene; 3-cyclohexen-l,2-ylene; 2, 5 -cyclohexadien- 1,4-ylene). These are examples of C5-6 cycloalkylene groups.

[0105] An example of a substituted C1-20 alkylene group is a C1-20 perfluoroalkylene group. A C1-20 perfluoroalkylene group is a perfluorinated C1-20 alkylene group. “Perfluorinated” in this context means completely fluorinated such that there are no carbon-bonded hydrogen atoms replaceable with fluorine.

[0106] C1-20 alkylene, C1-20 perfluoroalkylene, C1-20 alkyl, C1-20 haloalkyl, C1-20 fluoroalkyl and C1-20 perfluoroalkyl groups as defined herein are either uninterrupted or interrupted by one or more heteroatoms or heterogroups, such as S, O or N(R”) wherein R” is H, C1-6 alkyl or aryl (typically phenyl), or by one or more arylene groups. The arylene groups are typically phenylene, but may be perfluoroarylene groups, for instance tetrafluorophenylene. The phrase “optionally interrupted” as used herein thus refers to a C1-20 alkylene, C1-20 perfluoroalkylene, C1-20 alkyl, C1-20 haloalkyl, C1-20 fluoroalkyl or C1-20 perfluoroalkyl group, as defined above, which is uninterrupted or which is interrupted between adjacent carbon atoms by a heteroatom such as oxygen or sulfur, by a heterogroup such as N(R”) wherein R” is H, aryl or C1-6 alkyl, or by an arylene group. For instance, a C1-20 alkyl group such as n-butyl may be interrupted by the heterogroup N(R”) as

[0107] follows: -CH2N(R”)CH2CH2CH3, -CH2CH2N(R”)CH2CH3, or -CH2CH2CH2N(R”)CH3. Similarly, analkylene group such as n-butylene may be interrupted by the heterogroup N(R”) as

[0108] follows: -CH2N(R”)CH2CH2CH2- -CH2CH2N(R”)CH2CH2-, or -CH2CH2CH2N(R”)CH2-. Typically an interrupted group, for instance an interrupted CMO alkylene or C1-20 alkyl group, is interrupted by 1, 2 or 3 heteroatoms or heterogroups, or by 1, 2 or 3 arylene (typically phenylene) groups. More typically, an interrupted group, for instance an interrupted C O alkylene or C1-20 alkyl group, is interrupted by 1 or 2 heteroatoms or heterogroups, or by 1 or 2 arylene (typically phenylene) groups. For instance, a C1-20 alkyl group such as n-butyl may be interrupted by 2 heterogroups N(R”) as follows: -CH2N(R”)CH2N(R”)CH2CH3.

[0109] An arylene group is an unsubstituted or substituted bidentate moiety obtained by removing two hydrogen atoms, one from each of two different aromatic ring atoms of an aromatic compound, which moiety has from 5 to 14 ring atoms (unless otherwise specified). Typically, each ring has from 5 to 7 or from 5 to 6 ring atoms. An arylene group may be unsubstituted or substituted, for instance, as specified above for aryl. Typically a substituted heteroarylene group carries 1, 2 or 3 substituents, for instance 1 or 2.

[0110] In this context, the prefixes (e.g., C5-20, Ce-2o, C5-14, C5-7, C5-6, etc.) denote the number of ring atoms, or range of number of ring atoms, whether carbon atoms or heteroatoms. For example, the term "C5-6 arylene," as used herein, pertains to an arylene group having 5 or 6 ring atoms. Examples of groups of arylene groups include C5-20 arylene, Ce-2o arylene, C5-14 arylene, Ce-i4 arylene, Ce-io arylene, C5-12 arylene, C5-10 arylene, C5-7 arylene, C5-6 arylene, C5 arylene, and Ce arylene.

[0111] The ring atoms may be all carbon atoms, as in "carboarylene groups" (e.g., Ce-2o carboarylene, Ce-i4 carboarylene or Ce-io carboarylene).

[0112] Examples of Ce-2o arylene groups which do not have ring heteroatoms (i.e., Ce-2o carboarylene groups) include, but are not limited to, those derived from the compounds discussed above in regard to aryl groups, e.g. phenylene, and also include those derived from aryl groups which are bonded together, e.g. phenylene -phenylene (diphenylene) and phenylene-phenylene-phenylene (triphenylene).

[0113] Alternatively, the ring atoms may include one or more heteroatoms, as in "heteroarylene groups" (e.g., C5-10 heteroarylene). A heteroarylene group may be unsubstituted or substituted, for instance, as specified above for aryl. Typically a substituted heteroarylene group carries 1, 2 or 3 substituents, for instance 1 or 2.

[0114] Examples of heteroarylene groups include, but are not limited to, those derived from the compounds discussed above in regard to heteroaryl groups. Examples of heteroarylene groups include bidentate groups derived from pyridine, pyrazine, pyrimidine, pyridazine, furan, thiofuran, pyrazole, pyrrole, oxazole, oxadiazole, isoxazole, thiadiazole, thiazole, isothiazole, imidazole and pyrazole.

[0115] A perfluoroarylene group is a perfluorinated arylene group. “Perfluorinated” in this context means completely fluorinated such that there are no carbon-bonded hydrogen atoms replaceable with fluorine. Typically it is tetrafluorophenylene.As used herein the term halo is a group selected from -F, -Cl, -Br, and -I.

[0116] As used herein the term keto represents a group of formula: =0

[0117] As used herein the term nitro represents a group of formula: -NO2

[0118] As used herein the term cyano represents a group of formula: -CN

[0119] As used herein the term hydroxyl represents a group of formula: -OH

[0120] As used herein the term thiol represents a group of formula: -SH

[0121] As used herein the term sulfonyl represents a group of formula: -S(0)2R' wherein R' is a C1-10 alkyl group, preferably a C1-6 alkyl group, as defined previously.

[0122] As used herein the term acyl represents a group of formula: -C(=0)R, wherein R is an acyl substituent, for example, a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C3-20 heterocyclyl group, or a substituted or unsubstituted aryl group. Examples of acyl groups include, but are not limited to, -C(=0)CH3 (acetyl), -C(=O)CH2CH3 (propionyl), -C(=O)C(CH3)3 (t-butyryl), and -C(=O)Ph (benzoyl, phenone).

[0123] As used herein the term acyloxy (or reverse ester) represents a group of formula: -0C(=0)R, wherein R is an acyloxy substituent, for example, substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C3-2oheterocyclyl group, or a substituted or unsubstituted aryl group, typically a C1-6 alkyl group. Examples of acyloxy groups include, but are not limited to, -0C(=0)CH3 (acetoxy), -OC(=O)CH2CH3, -OC(=O)C(CH3)3, -OC(=O)Ph, and -OC(=O)CH2Ph.

[0124] As used herein the term ester (or carboxylate, carboxylic acid ester or oxycarbonyl) represents a group of formula: -C(=0)0R, wherein R is an ester substituent, for example, a substituted or unsubstituted C1-20 alkyl group (for instance a substituted or unsubstituted C1.4 alkyl group), a substituted or unsubstituted C3-20 heterocyclyl group, or a substituted or unsubstituted aryl group (typically a phenyl group). Examples of ester groups include, but are not limited

[0125] to, -C(=0)0CH3, -C(=O)OCH2CH3, -C(=O)OC(CH3)3, and -C(=O)OPh.

[0126] As used herein the term amino represents a group of formula -NH2. The term C1-C10 alkylamino represents a group of formula -NHR' wherein R' is a C1-10 alkyl group, preferably a C1-6 alkyl group, as defined previously. The term di(Ci-io)alkylamino represents a group of

[0127] formula -NR'R” wherein R' and R” are the same or different and represent C1-10 alkyl groups, preferably C1-6 alkyl groups, as defined previously. The term arylamino represents a group of formula -NHR' wherein R' is an aryl group, preferably a phenyl group, as defined previously. The term diarylamino represents a group of formula -NR'R' ' wherein R' and R' ' are the same or different and represent aryl groups, preferably phenyl groups, as defined previously. The term arylalkylamino represents a group of formula -NR'R' ' wherein R' is a C1-10 alkyl group, preferably a C1-6 alkyl group, and R” is an aryl group, preferably a phenyl group.

[0128] As used herein the term amido represents a group of formula: -C(=0)NR R ”, wherein R and R are independently H or amino substituents, as defined for di(Ci-io)alkylamino groups. Examples of amido groups include, but are not limitedto, -C(=O)NH2, -C(=O)NHCH3, -C(=O)N(CH3)2, -C(=O)NHCH2CH3, and -C(=O)N(CH2CH3)2, as well as amido groups in which R and R ”, together with the nitrogen atom to which they are attached, form a heterocyclic structure as in, for example, piperidinocarbonyl, morpholinocarbonyl, thiomorpholinocarbonyl, and piperazinocarbonyl.

[0129] As used herein, the terms “carboxy”, “carboxyl” and “carboxylic acid” each represent a group of the formula: -C(=O)OH, or -COOH. As would be understood by the skilled person, a carboxylic acid group (for instance, when employed in the present invention) can exist in protonated and deprotonated forms (for example, -C(=O)OH and -C(=O)O ), and in salt forms (for example, -C(=O)O X+, wherein X+is a monovalent cation).

[0130] As used herein the term acylamido represents a group of formula: -NRxC(=O)Ry, wherein Rxis an amide substituent, for example, hydrogen, a Ci.2oalkyl group, a C3.2o heterocyclyl group, an aryl group, preferably hydrogen or a C1-20 alkyl group, and Ryis an acyl substituent, for example, a C1-20 alkyl group, a C3.2o heterocyclyl group, or an aryl group, preferably hydrogen or a C1-20 alkyl group. Examples of acylamide groups include, but are not limited

[0131] to, -NHC(=O)CH3, -NHC(=O)CH2CH3, -NHC(=O)Ph, -NHC(=O)CI5H3I and -NHC(=O)C9HI9. Thus, a substituted C1-20 alkyl group may comprise an acylamido substituent defined by the

[0132] formula -NHC(=O)-CI.2Q alkyl, such as -NHC(=O)Ci5H3ior -NHC(=O)C9HI9. Rxand Rymay together form a cyclic structure, as in, for example, succinimidyl, maleimidyl, and phthalimidyl:

[0133]

[0134] succinimidyl maleimidyl phthalimidyl

[0135] A Ci-io alkylthio group is a said Ci-io alkyl group, preferably a Ci-6 alkyl group, attached to a thio group. An arylthio group is an aryl group, preferably a phenyl group, attached to a thio group.

[0136] A CI-2Q alkoxy group is a said substituted or unsubstituted C1-20 alkyl group attached to an oxygen atom. A Ci-io alkoxy group is a said substituted or unsubstituted Ci-io alkyl group attached to an oxygen atom. A Ci-6 alkoxy group is a said substituted or unsubstituted Ci-6 alkyl group attached to an oxygen atom. A C1-4 alkoxy group is a substituted or unsubstituted C1-4 alkyl group attached to an oxygen atom. Said C1-20, C1-10, C1-6 and C1.4 alkyl groups are optionally interrupted as defined herein. Examples of C1.4 alkoxy groups include, -OMe (methoxy), -OEt (ethoxy), -O(nPr) (n-propoxy), -O(iPr) (isopropoxy), -O(nBu) (n-butoxy), -O(sBu) (sec-butoxy), -O(iBu) (isobutoxy), and -O(tBu) (tert-butoxy). Further examples of C1-20 alkoxy groups are -O(Adamantyl), -O-CH2-Adamantyl and -O-CH2-CH2-Adamantyl. An aryloxy group is a substituted or unsubstituted aryl group, as defined herein, attached to an oxygen atom. An example of an aryloxy group is -OPh (phenoxy).

[0137] As used herein, the term “sulfonic acid” represents a group of the formula: -S(=O)2OH. As would be understood by the skilled person, a sulfonic acid group can exist in protonated anddeprotonated forms (for example, -S(=0)20H and -S(=0)20 ), and in salt forms (for example, -S(=O)2O X+, wherein X+is a monovalent cation).

[0138] As used herein, the term “sulfonamide” represents a group of formula:

[0139] -S(O)2NH2.

[0140] “Molecular weight” in the context of a polymer as described herein can be expressed as either a number average molecular weight (Mn), or a weight average molecular weight or a peak molecular weight. Unless otherwise indicated, all references to molecular weight of a polymer herein refer to the number average molecular weight. These molecular weight determinations, number average, weight average and peak, can be measured using gel permeation chromatography or other liquid chromatography techniques. Other methods for measuring molecular weight values can also be used, such as the use of end group analysis or the measurement of colligative properties (e.g., freezing point depression, boiling point elevation, or osmotic pressure) to determine number average molecular weight, or the use of light scattering techniques, ultracentrifugation or viscometry to determine weight average molecular weight. Unless otherwise indicated, all references to molecular weight herein refer to the number average molecular weight as measured by gel permeation chromatography.

[0141] Polymer for Treating a Surface

[0142] The invention provides a polymer for treating a surface, which polymer comprises: n reactive intermediate precursor groups, wherein n is an integer equal to or greater than 3; and m groups for controlling surface -initiated reversible-deactivation radical polymerization (SIRDRP), wherein m is an integer equal to or greater than 3. The groups for controlling SIRDRP are selected from groups which comprise an initiator and groups which comprise a chain transfer agent (CTA) .

[0143] The term “reactive intermediate precursor group”, as used herein, means a latent reactive group which is capable of being converted into a reactive intermediate group (specifically, into a carbene or nitrene reactive intermediate group) by a chemical process or by the application of energy, wherein the reactive intermediate group is capable of further reaction. The “application of energy” may for instance involve the application of thermal energy (i.e. heating) or irradiation, although any suitable source of energy can be used. The reactive intermediate groups are typically generated by a thermal process and / or by an irradiation process, but can be generated chemically. Typically, the reactive intermediate groups are generated by thermal irradiation, for instance by heating, especially when the groups are hydrazone or diazo groups and the reactive intermediate is a carbene reactive intermediate. This heat might be applied to the crosslinker compound externally, for example by using a hot press, but may also be as a result of another process, for example, extrusion. Alternatively, the reactive intermediate groups may be generated by electromagnetic radiation, for instance by UV, microwave or laser irradiation, or by ultrasonic irradiation.

[0144] The reactive intermediate precursor groups employed in the present invention are selected from carbene precursor groups and nitrene precursor groups. “Carbene precursor groups”, i.e. are capableof conversion into carbene reactive intermediates, whereas “nitrene precursor groups”, i.e. are capable of conversion into nitrene reactive intermediates.

[0145] The carbene precursor groups employed in the present invention are selected from hydrazone groups of formula (A), diazo groups of formula (B) and diazirine groups of formula (C), and the nitrene precursor groups are azide groups of formula (D):

[0146] wherein, in f

[0147]

[0148] 6 alkyl group or an unsubstituted or substituted aryl group.

[0149] The n reactive intermediate precursor groups in the polymer for treating a surface may be the same or different. For instance, the n reactive intermediate precursor groups in the polymer for treating a surface may all be carbene precursor groups, or they may all be nitrene precursor groups (i.e. azide groups of formula D), or some of them may be carbene precursor groups and the others may be nitrene precursor groups. Usually, however, the n reactive intermediate precursor groups in the crosslinker compound are either all nitrene groups (azide groups of formula D), or they are all carbene precursor groups. When the n reactive intermediate precursor groups in the crosslinker compound comprise carbene precursor groups, the carbene precursor groups may be the same or different and may be independently selected from hydrazone groups of formula (A), diazo groups of formula (B) and diazirine groups of formula (C) . Often, however, each of the carbene precursor groups is the same, for instance they may all be hydrazone groups of formula (A), or they may all be diazo groups of formula (B), or they may all be diazirine groups of formula (C).

[0150] Often, the reactive intermediate precursor groups employed in the present invention are carbene precursor groups. The carbene precursor groups are often hydrazone groups of formula (A) or diazo groups of formula (B). More typically, the carbene precursor groups are hydrazone groups of formula (A). Hydrazone groups of formula (A) in which R1is -S(O)2R2are particularly preferred. Often, R2is tolyl, typically para-tolyl, and therefore R1is often a tosyl group.

[0151] Carbene or nitrene reactive intermediate groups may be generated from the reactive intermediate precursor groups of the polymer, so that the carbene or nitrene reactive intermediate groups can react a surface of a substrate, and bond the polymer to that surface, and thereby functionalise the surface of the substrate with the polymer. The substrate is thereby provided with a surface that is functionalised with groups for controlling SIRDRP, so that the substrate has a surface suitable for performing SIRDRP thereon. The polymer of the invention is therefore suitable for treating a surface, hence the term “polymer for treating a surface”. It may also be termed a surface treatment polymer. Once generated, the reactive intermediate (carbene or nitrene) groups of thepolymer typically also react with other molecules of the polymer to crosslink the polymer to itself (and indeed to any other molecules present). The polymer of the invention may also therefore be referred to as a crosslinker or a crosslinker compound. The polymer often therefore reacts both with the surface of the substrate, to bond the polymer to the surface, and also with other polymer molecules, to crosslink the polymer. In this way a robust and stable surface treatment in preparation for SIRDRP is provided which is applicable both to inert substrates and active ones.

[0152] The number of reactive intermediate precursor groups in the polymer for treating a surface, n, is an integer equal to or greater than 3. Often, however, n is an integer greater than or equal to 4. Preferably, n is an integer equal to or greater than 5.

[0153] In one embodiment, n is an integer of from 3 to 50, more typically an integer of from 3 to 30, or from 3 to 20, or from 3 to 10. n may for instance be an integer of from 4 to 50, more typically an integer of from 4 to 30, or from 4 to 20, or from 4 to 10. Preferably, n is an integer of from 5 to 50, for instance an integer of from 5 to 30, for instance from 5 to 20, or from 5 to 10.

[0154] Having five or more reactive intermediate precursor groups (i.e. n being at least 5) is preferable to having only 4 such groups, which is in turn preferable to having only three such groups, because having at least 5 such groups further enhances curing and crosslinking in 3 dimensions, further promoting the formation of a long-range crosslinked network post curing. This further reduces the probability of having ungrafted material, such as dimers and other side products, in the surface coating, removing the need to wash the surface thoroughly to remove loose material using harsh organic solvents, making the process both more cost effective and environmentally friendly. It also further increases the cross-link density which imparts further stability in both water and organic solvents, and typically also in harsher conditions such as strong acid or base.

[0155] In other embodiments, however, n is an integer of from 3 to 500, and is more typically an integer of from 4 to 200, and preferably from 5 to 100. For instance n may be from 10 to 100, for instance from 10 to 50. In yet other embodiments, n may be an integer equal to or greater than 50, for instance equal to or greater than 100. Thus, n may be an integer of from 50 to 1,000,000, from 50 to 100,000, from 50 to 10,000, from 50 to 5,000, or from 50 to 1,000. More typically, in this embodiment, n is an integer of from 50 to 1,000.

[0156] The n reactive intermediate precursor groups employed in the polymer of the invention may be nitrene precursor groups, i.e. azide groups of formula (D). The decomposition of azide groups to form reactive nitrene intermediate groups is thought to occur by elimination of dinitrogen to form the reactive nitrene intermediate. As discussed above, this can be initiated by the application of energy, typically by heating or by irradiation. Alternatively, the reactive nitrene intermediate can be generated chemically.

[0157] Often, however, the n reactive intermediate precursor groups employed in the polymer of the invention are carbene precursor groups.Thus, typically, the reactive intermediate precursor groups of the polymer of the invention are carbene precursor groups selected from hydrazone groups of formula (A), diazo groups of formula (B) and diazirine groups of formula (C):

[0158]

[0159] wherein R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-6 alkyl group or an unsubstituted or substituted aryl group.

[0160] The carbene precursor groups may be diazirine groups of formula (C). The decomposition of such diazirine groups to form reactive carbene intermediate groups is thought to occur by elimination of dinitrogen to form the reactive carbene intermediate. As discussed above, this can be initiated by the application of energy, typically by heating or by irradiation. Alternatively, the reactive carbene intermediate can be generated chemically.

[0161] Often, however, the carbene precursor groups are selected from hydrazone groups of formula (A) and diazo groups of formula (B).

[0162] The carbene precursor groups may for instance be diazo groups of formula (B). The decomposition of such diazo groups to form reactive carbene intermediate groups is thought to occur by elimination of dinitrogen to form the reactive carbene intermediate. As discussed above, this can be initiated by the application of energy, typically by heating or by irradiation. Alternatively, the reactive carbene intermediate can be generated chemically.

[0163] Preferably, however, the carbene precursor groups are hydrazone groups of formula (A).

[0164] In the hydrazone groups of formula (A), R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-6 alkyl group or an unsubstituted or substituted aryl group.

[0165] Often, R1is H.

[0166] However, hydrazone groups of formula (A) in which R1is -S(O)2R2are often preferred.

[0167] Typically, R2is an unsubstituted or substituted Ci-6 alkyl group, an unsubstituted or substituted phenyl group, or an unsubstituted or substituted naphthyl group. Often, R2is Ci-6 alkyl, phenyl or naphthyl, which phenyl or naphthyl is unsubstituted or substituted with Ci-6 alkyl, di(Ci-e alkyl)amino, hydroxyl, nitro, cyano or methoxy.

[0168] More typically, R2is Ci-6 alkyl, phenyl or naphthyl, which phenyl or naphthyl is unsubstituted or substituted with Ci-6 alkyl or di(Ci-e alkyl)amino.

[0169] Typically, R1is -S(O)2R2wherein R2is phenyl substituted with Ci-6 alkyl. More typically, R1is -S(O)2R2wherein R2is phenyl substituted with methyl (i.e. tolyl, typically para-tolyl). Thus, often, R1is a tosyl group. In another embodiment, R1is H.Hydrazone groups of formula (A) are “carbene precursor groups”, because they are capable of conversion into carbene reactive intermediates. When R1is H this conversion may be achieved by oxidation of the hydrazone to a diazomethane followed by the application of energy, typically by heating or by irradiation. When R1is -S(O)2R2conversion of the N-sulfonylhydrazone group into the carbene reactive intermediate may be achieved by the application of energy, typically by heating or by irradiation (for instance by electromagnetic radiation, for instance by UV, microwave or laser irradiation, or by ultrasonic irradiation). The conversion is often achieved by the application of heat. The heat might be applied to the crosslinker compound externally, for example by using a hot press, but may also be as a result of another process, for example, extrusion. Additionally or alternatively, the conversion may be achieved chemically. For instance, conversion of the N-sulfonylhydrazone group into the carbene reactive intermediate may be achieved by treatment with a base followed by the application of energy, typically by heating or by irradiation. Any suitable base may be used, for instance an organic base such as a trialkyl amine (e.g. triethylamine) or l,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Alternatively an inorganic base may be used, such as an alkali metal hydroxide, e.g. sodium, lithium or potassium hydroxide. The decomposition of the sulfonyl hydrazone to the carbene is thought to occur by elimination of R1, to form a diazo intermediate group, and subsequent elimination of dinitrogen to form the reactive carbene intermediate. Accordingly, the carbene precursor groups may be hydrazone groups of formula (A) as defined above.

[0170] Thus, often, the reactive intermediate precursor groups of the polymer of the invention are carbene precursor groups selected from hydrazone groups of formula (A), diazo groups of formula (B) and diazirine groups of formula (C):

[0171]

[0172] wherein R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-6 alkyl group or an unsubstituted or substituted aryl group.

[0173] Alternatively, the reactive intermediate precursor groups of the polymer of the invention are nitrene precursor groups, which are azide groups of formula (D):

[0174]

[0175] As discussed above, the polymer of the invention for treating a surface comprises m groups for controlling surface -initiated reversible-deactivation radical polymerization (SIRDRP), wherein m is an integer equal to or greater than 3. Surface initiated reversible -deactivation radicalpolymerization (SIRDRP) is a technique that allows growth of polymers from surfaces with control over molecular weight and polydispersity. This control is essential when grafting on porous substrates, such as porous membranes, or porous particles, as it prevents unwanted blocking of the pore structure due to uncontrolled polymer growth. For SIRDRP either an initiator or chain transfer agent (CTA) needs to be present on the surface. Thus, in the polymer of the invention the groups for controlling SIRDRP are selected from groups which comprise an initiator and groups which comprise a chain transfer agent (CTA).

[0176] The m groups for controlling SIRDRP in the polymer of the invention may be the same or different. For instance, the m groups for controlling SIRDRP in the polymer may all be groups which comprise an initiator for SIRDRP, or they may all be groups which comprise a CTA for SIRDRP, or some of them may be groups which comprise an initiator and the others may be groups which comprise a CTA. Usually, however, the m groups for controlling SIRDRP in the polymer are either all groups which comprise an initiator, or they are all groups which comprise a CTA.

[0177] Indeed, the initiator or CTA employed in the polymer of the invention is typically chosen based on the type of SI-RDRP that is to be carried out after the surface of a substrate has been treated with a surface treatment polymer of the invention. Secondly, the choice of initiator or CTA is dictated based on the monomer intended to be polymerised, and the rate and efficiency of the polymerisation of that monomer that one wishes to achieve. A wide variety of initiators and CTAs are known in the art of RDRP and SI-RDRP to achieve polymerisation of a wide variety of monomers and reaction rates thereof. See for instance https: / / www.sigmaaldrich.com / GB / en / technical-documents / protocol / materials-science-and-engineering / polymer-synthesis / concepts-and-tools-for-raft-polymerization which describes a variety of RAFT agents suitable for various monomer types. See also https: / / www.cmu.edu / maty / development-atrp / understanding_mechanistic_parameters.html which summarises the activation rate constants (kact) determined for a variety of initiators for Cu-mediated ATRP under the same conditions (as described in Tang, W.; Kwak, Y.; Braunecker, W.; Tsarevsky, N. V.; Coote, M. L.; Matyjaszewski, K. J. Am. Chem. Soc. 2008, 130, 10702-10713; and Tang, W. In Chemistry of Synthetic High Polymers; Carnegie -Mellon Univ.: Pittsburgh, PA, USA, 2008; p 304 pp.; and Tang, W.; Matyjaszewski, K. Macromolecules 2007, 40, 1858-1863). The present invention is versatile in that it allows for the incorporation of any of these different initiators or CTA’s to suit any individual application.

[0178] Many different types of reversible -deactivation radical polymerization (RDRP) are known in the art, and for each of those different types of RDRP, suitable initiator and CTA moieies are known. A group comprising any one of these initiator or CTA moieties may be employed in the polymer of the invention as the groups for controlling SIRDRP.

[0179] The RDRP of interest may for instance be atom transfer radical polymerisation (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerisation, photoiniferter-mediated polymerisation (PIMP), nitroxide -mediated radical polymerisation (NMP), iniferter polymerisation,catalytic chain transfer polymerisation, cobalt mediated radical polymerisation (CMRP), iodine-transfer polymerization (ITP) or copper-based reversible-deactivation radical polymerization (Cu-based RDRP). Thus, the groups for controlling SIRDRP in the polymer of the invention may be groups which comprise an initiator suitable for any of the aforementioned types of RDRP. Similarly, the groups for controlling SIRDRP in the polymer of the invention may be groups which comprise a CTA suitable for any of the aforementioned types of RDRP. Thus, often, the groups for controlling SIRDRP, in the polymer of the invention, are selected from groups which comprise an initiator suitable for any of the aforementioned types of RDRP and groups which comprise a CTA suitable for any of the aforementioned types of RDRP.

[0180] The groups for controlling SIRDRP in the polymer of the invention may, for instance, be groups which comprise an initiator suitable for ATRP (an initiator suitable for ATRP may be referred to herein as an “initiator for ATRP” or an “ATRP initiator”). Similarly, the groups for controlling SIRDRP in the polymer of the invention may be groups which comprise a CTA suitable for ATRP (a CTA suitable for ATRP may be referred to herein as a “CTA for ATRP” or an “ATRP CTA”).

[0181] Often, the groups for controlling SIRDRP in the polymer of the invention are ATRP initiators.

[0182] Alternatively, the groups for controlling SIRDRP in the polymer of the invention may, for instance, be groups which comprise an initiator suitable for RAFT (an initiator suitable for RAFT may be referred to herein as an “initiator for RAFT” or a “RAFT initiator”). Similarly, the groups for controlling SIRDRP in the polymer of the invention may be groups which comprise a CTA suitable for RAFT (a CTA suitable for RAFT may be referred to herein as a “CTA for RAFT” or a “RAFT CTA” or simply a “RAFT agent”). The groups for controlling SIRDRP may be selected from RAFT initiators and RAFT CTAs.

[0183] Alternatively, the groups for controlling SIRDRP in the polymer of the invention may, for instance, be groups which comprise an initiator suitable for PIMP (an initiator suitable for PIMP may be referred to herein as an “initiator for PIMP” or a “PIMP initiator”). Similarly, the groups for controlling SIRDRP in the polymer of the invention may be groups which comprise a CTA suitable for PIMP (a CTA suitable for PIMP may be referred to herein as a “CTA for PIMP” or a “PIMP CTA”). The groups for controlling SIRDRP may be selected from PIMP initiators and PIMP CTAs.

[0184] Alternatively, for instance, the groups for controlling SIRDRP in the polymer of the invention may be groups which comprise an initiator suitable for NMP (an initiator suitable for NMP may be referred to herein as an “initiator for NMP” or a “NMP initiator”). Similarly, the groups for controlling SIRDRP in the polymer of the invention may be groups which comprise a CTA suitable for NMP (a CTA suitable for NMP may be referred to herein as a “CTA for NMP” or a “NMP CTA”). The groups for controlling SIRDRP may be selected from NMP initiators and NMP CTAs.

[0185] The groups for controlling SIRDRP in the polymer of the invention may be groups which comprise an initiator suitable for iniferter polymerisation. As the skilled person will appreciate, an “iniferter” is a chemical moiety that can act as initiator, transfer agent and terminator. Thus, aninitiator suitable for iniferter polymerisation will generally be an iniferter. Thus, the groups for controlling SIRDRP in the polymer of the invention may be groups which comprise an iniferter.

[0186] Alternatively, the groups for controlling SIRDRP in the polymer of the invention may be groups which comprise an initiator suitable for CMRP (an initiator suitable for CMRP may be referred to herein as an “initiator for CMRP” or a “CMRP initiator”). Similarly, the groups for controlling SIRDRP in the polymer of the invention may be groups which comprise a CTA suitable for CMRP (a CTA suitable for CMRP may be referred to herein as a “CTA for CMRP” or a “CMRP CTA”). The groups for controlling SIRDRP may be selected from CMRP initiators and CMRP CT As.

[0187] The groups for controlling SIRDRP in the polymer of the invention may alternatively be groups which comprise an initiator suitable for ITP (an initiator suitable for ITP may be referred to herein as an “initiator for ITP” or a “ITP initiator”). Similarly, the groups for controlling SIRDRP in the polymer of the invention may be groups which comprise a CTA suitable for ITP (a CTA suitable for ITP may be referred to herein as a “CTA for ITP” or a “ITP CTA”). The groups for controlling SIRDRP may be selected from ITP initiators and ITP CTAs.

[0188] The groups for controlling SIRDRP in the polymer of the invention may alternatively be groups which comprise an initiator suitable for Cu-based RDRP (an initiator suitable for Cu-based RDRP may be referred to herein as an “initiator for Cu-based RDRP” or a “Cu-based RDRP initiator”). Similarly, the groups for controlling SIRDRP in the polymer of the invention may be groups which comprise a CTA suitable for Cu-based RDRP (a CTA suitable for ITP may be referred to herein as a “CTA for Cu-based RDRP” or a “Cu-based RDRP CTA”). The groups for controlling SIRDRP may be selected from Cu-based RDRP initiators and Cu-based RDRP CTAs.

[0189] Often, in the polymer of the invention, the groups for controlling SIRDRP are groups which comprise an initiator for atom transfer radical polymerisation (ATRP).

[0190] The groups for controlling SIRDRP may however be groups which comprise a CTA for reversible addition-fragmentation chain transfer (RAFT) polymerisation and / or groups which comprise an initiator for RAFT polymerisation.

[0191] The groups for controlling SIRDRP may be groups which comprise an initiator for photoiniferter-mediated polymerisation (PIMP) and / or groups which comprise a CTA for PIMP. The initiator or CTA for PIMP may be an iniferter, for instance a photoiniferter.

[0192] The groups for controlling SIRDRP may be groups which comprise an initiator for nitroxide-mediated radical polymerisation (NMP).

[0193] The groups for controlling SIRDRP may be groups which comprise an initiator for iniferter polymerisation, wherein the initiator is an iniferter.

[0194] The groups for controlling SIRDRP may be groups which comprise a CTA for catalytic chain transfer polymerisation and / or groups which comprise an initiator for catalytic chain transfer polymerisation.The groups for controlling SIRDRP may be groups which comprise a CTA for cobalt mediated radical polymerisation (CMRP) and / or groups which comprise an initiator for CMRP.

[0195] The groups for controlling SIRDRP may be groups which comprise a CTA for iodine -transfer polymerization (ITP) and / or groups which comprise an initiator for ITP.

[0196] The groups for controlling SIRDRP may be groups which comprise an initiator for copperbased reversible-deactivation radical polymerization (Cu-based RDRP) and / or groups which comprise a CTA for Cu-based RDRP.

[0197] Generally, m, i.e. the number of groups for controlling SIRDRP in the polymer of the invention is an integer equal to or greater than 3. Preferably, m is greater than 3, i.e. an integer equal to or greater than 4. This is generally desirable in order to maintain a good loading of groups for controlling SIRDRP in the polymer. Indeed m is often an integer equal to or greater than 5.

[0198] Typically, in the polymer of the invention, the ratio of the number of reactive intermediate precursor groups, n, in the polymer, to the number of groups for controlling SIRDRP, m, in the polymer, n:m, is at least 0.5: 1, and is preferably at least 1:1. In some embodiments n:m is 1:1. Often, for instance, the ratio n:m is at least 1.2:1, for instance at least 1.5:1. For instance, n:m may be from 0.5 : 1 to 5 : 1 , for instance from 1 : 1 to 3 : 1 , or from 1 : 1 to 2 : 1. The se ratio range s reflect the fact that, often, in preferred embodiments of the polymer of the invention, m is less than n, or at least m is not very much greater than n. This is because relatively low loadings of the groups for controlling SIRDRP may be required in order to control polymer growth / grafting to the required level when SIRDRP is carried out from a surface functionalised with the polymer of the invention. At the same time, it is often desirable to have higher levels of the reactive intermediate precursor groups in the polymer to ensure that strong bonding to the substrate and long-range crosslinking in three dimensions occurs during curing.

[0199] The number of groups for controlling SIRDRP in the polymer of the invention, m, may for instance be an integer of from 3 to 50, for instance an integer of from 3 to 30, or from 3 to 20, or from 3 to 10. The integer m may for instance be from 4 to 50, for instance from 4 to 30, or from 4 to 20, or from 4 to 10. Preferably, m is an integer of from 5 to 50, for instance an integer of from 5 to 30, for instance from 5 to 20, or from 5 to 10. In other embodiments, however, m may be an integer of from 3 to 500, for instance an integer of from 4 to 200, and preferably from 5 to 100. For instance, m may be from 10 to 100, for instance from 10 to 50. In yet other embodiments, m may be an integer equal to or greater than 50, for instance equal to or greater than 100. Thus, m may be an integer of from 50 to 1,000,000, from 50 to 100,000, from 50 to 10,000, from 50 to 5,000, or from 50 to 1,000. More typically, in this embodiment, m is an integer of from 50 to 1,000.

[0200] Types of SIRDRP that are of particular interest include surface -induced ATRP (SI-ATRP), surface -induced RAFT polymerisation (SI-RAFT), surface -induced PIMP (SI-PIMP) and surface-induced NMP (SI-NMP).

[0201] Thus, typically, in the polymer of the invention the groups for controlling SIRDRP are:groups which comprise an initiator for atom transfer radical polymerisation (ATRP); groups which comprise a CTA for reversible addition-fragmentation chain transfer (RAFT) polymerisation and / or groups which comprise an initiator for RAFT polymerisation; groups which comprise an initiator for photoiniferter-mediated polymerisation (PIMP) and / or groups which comprise a CTA for PIMP; or groups which comprise an initiator for nitroxide-mediated radical polymerisation (NMP).

[0202] Thus, the groups for controlling SIRDRP may be groups which comprise an initiator for ATRP. The groups which comprise an ATRP initiator may be selected from groups comprising any one of the following “ATRP moieties” (i), (ii), (iii), (iv), (v) and (vi).

[0203] • ATRP moiety (i):

[0204]

[0205] wherein:

[0206] R1is hydrogen or an unsubstituted or substituted group selected from C O alkyl, aryl, heteroaryl and ester; R2is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; and X1is Br, Cl or I.

[0207] Preferably X1is Br or Cl. More preferably, X1is Br.

[0208] Often, R1is hydrogen or an unsubstituted group selected from CMO alkyl, aryl, heteroaryl and ester, and R2is hydrogen or an unsubstituted group selected from C O alkyl, aryl and heteroaryl.

[0209] Typically, R1and R2are independently selected from hydrogen and unsubstituted C1-4 alkyl. For instance, R1and R2may be independently selected from hydrogen, methyl and ethyl, for instance from hydrogen and methyl. Often, R1and R2are both H, or R1is methyl and R2is H.

[0210] Alternatively, R1is often an ester, for instance -C(O)ORewherein Reis unsubstituted C1-4 alkyl, and R2is typically H. For instance, R1may be -C(O)OMe or -C(O)OEt and R2may be H.

[0211] • ATRP moieties (ii) and (iii):

[0212]

[0213] wherein:

[0214] each of R3, R4and R5independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; and X2is Br, Cl or I.Each of R42and R52independently is hydrogen or an unsubstituted or substituted group selected from C O alkyl, aryl and heteroaryl. Often, Each of R42and R52independently is hydrogen or an unsubstituted C1-4 alkyl. Usually, each of R42and R52is H.

[0215] Preferably X2is Br or Cl. More preferably, X2is Br.

[0216] Typically, each of R3, R4and R5independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl. R3is often H or unsubstituted or substituted CMO alkyl. For instance, R3is often H or unsubstituted or substituted C1.4 alkyl. The substituted C O alkyl (or C1.4 alkyl) may be aryl-substituted CMO alkyl (or aryl-substituted C1.4 alkyl), for instance phenylsubstituted CMO alkyl (or phenyl-substituted C1-4 alkyl), such as, for instance, benzyl. R3may for instance be H or unsubstituted or substituted C1-2 alkyl. R3may for instance be H or unsubstituted or substituted methyl. For instance, R3may be H, methyl or phenyl-substituted methyl (i.e. benzyl). Often, R3is H or benzyl. R3may be H. R3may be benzyl. Often, R4and R5are independently selected from hydrogen and unsubstituted C1.4 alkyl. For instance, R4and R5may be independently selected from hydrogen, methyl and ethyl, for instance from hydrogen and methyl. Often, both of R4and R5are unsubstituted C1-4 alkyl. For instance, R4and R5are preferably both methyl groups. Alternatively, R4may be H and R5may be methyl, or R4and R5are both H. Often, R3is H, R4is methyl and R5is methyl. Often, R3is benzyl, R4is methyl and R5is methyl.

[0217] Typically, each of R3, R4and R5independently is hydrogen or an unsubstituted group selected from CMO alkyl, aryl and heteroaryl. For instance, R3is often H or unsubstituted C1-4 alkyl, for example R3is often H or methyl. Often, R4and R5are independently selected from hydrogen and unsubstituted C1.4 alkyl. For instance, R4and R5may be independently selected from hydrogen, methyl and ethyl, for instance from hydrogen and methyl. Often, both of R4and R5are unsubstituted C1-4 alkyl. For instance, R4and R5are preferably both methyl groups. Alternatively, R4may be H and R5may be methyl, or R4and R5are both H.

[0218] • ATRP moieties (iv) and (v):

[0219]

[0220] wherein:

[0221] each of R6and R7independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; and

[0222] X3is Br, Cl or I.

[0223] Each of R62and R72independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl. Often, Each of R62and R72independently is hydrogen or an unsubstituted C1-4 alkyl. Usually, each of R62and R72is H.Preferably X3is Br or Cl. More preferably, X3is Br.

[0224] Typically, each of R6and R7independently is hydrogen or an unsubstituted group selected from Ci-io alkyl, aryl and heteroaryl. Often, R6and R7are independently selected from hydrogen and unsubstituted C1.4 alkyl. For instance, R6and R7may be independently selected from hydrogen, methyl and ethyl, for instance from hydrogen and methyl. Often, both of R6and R7are unsubstituted C1-4 alkyl. For instance, R6and R7are preferably both methyl groups. Alternatively, R6may be H and R6may be methyl, or R6and R7are both H.

[0225] • ATRP moiety (vi):

[0226]

[0227] wherein

[0228] R8is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; and

[0229] X4is Br or Cl.

[0230] Typically, R8is hydrogen or an unsubstituted group selected from CMO alkyl, aryl and heteroaryl. For instance, R8is often hydrogen or unsubstituted C1.4 alkyl. R8may be H or methyl. Typically, R8is H.

[0231] The groups for controlling SIRDRP may be groups which comprise a CTA or initiator for RAFT polymerisation. The groups which comprise a CTA or initiator for RAFT polymerisation may be selected from groups comprising any one of the following “RAFT moieties” (i), (ii), (iii), (iv), (v), (vi), (vii), (viii), (ix) and (x).

[0232] • RAFT moieties (i) and (ii):

[0233]

[0234] wherein:

[0235] Z is -CH2O-, -CH2N(RV)-, O or N(RV) wherein Rvis hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;

[0236] Ar1is an unsubstituted or substituted group selected from aryl and heteroaryl; and

[0237] R10is unsubstituted or substituted C1-20 alkyl.Often, Z is N(RV). In other embodiments, however, Z may be O. Also, often, Z is -CH2O-. Rvis typically hydrogen or an unsubstituted group selected from C O alkyl, aryl and heteroaryl. Rvis typically hydrogen or an unsubstituted C1-6 alkyl group, for instance H or unsubstituted C1.4 alkyl. Rvis often H, methyl or ethyl. Most typically, Rvis H.

[0238] Ar1may be an unsubstituted or substituted aryl group, for instance unsubstituted or substituted phenyl. Ar1is often an unsubstituted group selected from aryl and heteroaryl. Ar1is often an unsubstituted aryl group, for instance unsubstituted phenyl.

[0239] R10may be unsubstituted or substituted CMO alkyl, for instance unsubstituted or substituted C1-4 alkyl. Often, however, R10is unsubstituted C1-20 alkyl. R10may for instance be unsubstituted Ci-10 alkyl, for instance unsubstituted C1-6 alkyl or unsubstituted C1-4 alkyl. R10is often methyl or ethyl. Typically, R10is methyl.

[0240] • RAFT moieties (iii) and (iv):

[0241]

[0242] wherein:

[0243] each of R11, R12, R13and R14independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; and

[0244] Ar2is an unsubstituted or substituted group selected from aryl and heteroaryl.

[0245] Ar2may be an unsubstituted or substituted aryl group, for instance unsubstituted or substituted phenyl. Ar2is often an unsubstituted group selected from aryl and heteroaryl. Ar2is often an unsubstituted aryl group, for instance unsubstituted phenyl.

[0246] Typically, R11and R12are independently selected from hydrogen and unsubstituted C1.4 alkyl. For instance, R11and R12may be independently selected from hydrogen, methyl and ethyl, for instance from hydrogen and methyl. Often, R11and R12are both H, or both methyl, or R11is methyl and R12is H.

[0247] Typically, R13and R14are independently selected from hydrogen and unsubstituted C1.4 alkyl. For instance, R13and R14may be independently selected from hydrogen, methyl and ethyl, for instance from hydrogen and methyl. Often, R13and R14are both H, or both methyl, or R13is methyl and R14is H.

[0248] RAFT moiety (v):

[0249]

[0250] wherein:

[0251] LRis unsubstituted or substituted C1-20 alkylene, which C1-20 alkylene is optionally interrupted by O, OC(O) or N(R”)C(O) wherein R” is H, Ci-e alkyl or aryl; and

[0252] RRis unsubstituted or substituted C1-20 alkyl.

[0253] LRis often unsubstituted or substituted C1-10 alkylene, for instance unsubstituted or substituted C1-6 alkylene, or unsubstituted or substituted C1-4 alkylene. Typically, when LRis substituted, it is substituted with a cyano group (CN) and / or with at least one unsubstituted C1.4 alkyl group, for instance at least one methyl group. For instance, LRmay be substituted with both a cyano group and an unsubstituted C1-4 alkyl group, or with two unsubstituted C1.4 alkyl groups. LRmay for instance be substituted with both a cyano group and a methyl group. LRmay for instance be substituted with two methyl groups. LRmay for instance be a dimethyl methylene group, i.e. -C(CH3)2-. Often, however, LRis unsubstituted. LRis often unsubstituted C1-6 alkylene, for instance unsubstituted C1.4 alkylene, or unsubstituted C1-3 alkylene. For instance, LRmay methylene. LRis often uninterrupted. However, LRmay be interrupted by O, for instance, or by OC(O) or N(R”)C(O) wherein R” is H, C1-6 alkyl or aryl.

[0254] RRis often unsubstituted C1-20 alkyl. It may for instance be unsubstituted C5-15 alkyl. For example, RRmay be a -C12H25 group, i.e. a dodecyl group.

[0255] RRmay be an unsubstituted or substituted C1-6 alkyl group. RRmay for instance be an aryl- or heteroaryl- substituted C1-6 alkyl group such as, for instance, benzyl. RRmay for instance be substituted with an ester group, for instance -C(0)0CH3. RRmay for instance be substituted with both an aryl group and an ester group; for instance, RRmay be -CH(Ph)C(O)OCH3. Alternatively, RRmay be an unsubstituted C1-6 alkyl group.

[0256] • RAFT moiety (vi):

[0257]

[0258] wherein:

[0259] Z is -CH2O-, -CH2N(RV)-, O or N(RV) wherein Rvis hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;

[0260] RRis unsubstituted or substituted C1-20 alkyl; and

[0261] Lsis unsubstituted or substituted C1-20 alkylene.

[0262] Often, Z is N(RV). In other embodiments, however, Z may be O. Often, Z is -CH2O-.Rvis typically hydrogen or an unsubstituted group selected from C O alkyl, aryl and heteroaryl. Rvis typically hydrogen or an unsubstituted Ci-6 alkyl group, for instance H or unsubstituted C1.4 alkyl. Rvis often H, methyl or ethyl. Most typically, Rvis H.

[0263] Lsis often unsubstituted or substituted CMO alkylene, for instance unsubstituted or substituted C1-6 alkylene, or unsubstituted or substituted C1-4 alkylene. Typically, when Lsis substituted, it is substituted with a cyano group (CN) and / or with at least one unsubstituted C1.4 alkyl group, for instance at least one methyl group. For instance, Lsmay be substituted with both a cyano group and an unsubstituted C1-4 alkyl group, or with two unsubstituted C1.4 alkyl groups. Lsmay for instance be substituted with both a cyano group and a methyl group. Lsmay for instance be a C2-4 alkylene group substituted with both a cyano group and a methyl group. Lsmay for instance be a -CH2-CH2-C(CHs)(CN)- group. Alternatively, Lsmay be substituted with two methyl groups. Lsmay for instance be a dimethyl methylene group, i.e. -C(CH3)2-.

[0264] RRis often unsubstituted C1-20 alkyl. It may for instance be unsubstituted C5-15 alkyl. For example, RRmay be a -C12H25 group, i.e. a dodecyl group.

[0265] RRmay be an unsubstituted or substituted C1-6 alkyl group. RRmay for instance be an aryl- or heteroaryl- substituted C1-6 alkyl group such as, for instance, benzyl. RRmay for instance be substituted with an ester group, for instance -C(0)0CH3. RRmay for instance be substituted with both an aryl group and an ester group; for instance, RRmay be -CH(Ph)C(O)OCH3. Alternatively, RRmay be an unsubstituted C1-6 alkyl group.

[0266] • RAFT moiety (vii):

[0267]

[0268] wherein:

[0269] LRis unsubstituted or substituted C1-20 alkylene, which C1-20 alkylene is optionally interrupted by O, OC(O) or N(R”)C(O) wherein R” is H, C1-6 alkyl or aryl; and

[0270] each of Ruand RTindependently is an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl.

[0271] LRis often unsubstituted or substituted C O alkylene, for instance unsubstituted or substituted C1-6 alkylene, or unsubstituted or substituted C1-4 alkylene. Typically, when LRis substituted, it is substituted with a cyano group (CN) and / or with at least one unsubstituted C1.4 alkyl group, for instance at least one methyl group. For instance, LRmay be substituted with both a cyano group and an unsubstituted C1-4 alkyl group, or with two unsubstituted C1.4 alkyl groups. LRmay for instance be substituted with both a cyano group and a methyl group. LRmay for instance be substituted with two methyl groups. LRmay for instance be a dimethyl methylene group, i.e. -C(CH3)2-. Often, however,LRis unsubstituted. LRis often unsubstituted Ci-6 alkylene, for instance unsubstituted C1.4 alkylene, or unsubstituted C1-3 alkylene. For instance, LRmay methylene. LRis often uninterrupted. However, LRmay be interrupted by O, for instance, or by OC(O) or N(R”)C(O) wherein R” is H, C1-6 alkyl or aryl

[0272] Often, each of Ruand RTis independently an unsubstituted or substituted group selected from C1-6 alkyl and aryl. For instance, each of Ruand RTmay be independently selected from unsubstituted or substituted C1-6 alkyl and phenyl. Often, each of Ruand RTis independently selected from unsubstituted C1-6 alkyl and phenyl. For instance, often Ruis phenyl and RTis unsubstituted C1-6 alkyl. For instance, Rumay be phenyl and RTmay be methyl, ethyl or propyl. Alternatively, Ruand RTmay both be unsubstituted C1-6 alkyl, for instance they may both be methyl, ethyl or propyl, or for instance they may both be ethyl.

[0273] • RAFT moiety (viii):

[0274]

[0275] wherein:

[0276] Z is -CH2O-, -CH2N(RV)-, O or N(RV) wherein Rvis hydrogen or an unsubstituted or substituted group selected from C1-10 alkyl, aryl and heteroaryl;

[0277] Lsis unsubstituted or substituted C1-20 alkylene;

[0278] each of Ruand RTindependently is an unsubstituted or substituted group selected from Ci-w alkyl, aryl and heteroaryl.

[0279] Often, Z is N(RV). In other embodiments, however, Z may be O. Often, Z is -CH2O-.

[0280] Rvis typically hydrogen or an unsubstituted group selected from C1-10 alkyl, aryl and heteroaryl. Rvis typically hydrogen or an unsubstituted C1-6 alkyl group, for instance H or unsubstituted C1.4 alkyl. Rvis often H, methyl or ethyl. Most typically, Rvis H.

[0281] Lsis often unsubstituted or substituted C1-10 alkylene, for instance unsubstituted or substituted C1-6 alkylene, or unsubstituted or substituted C1-4 alkylene. Typically, when Lsis substituted, it is substituted with a cyano group (CN) and / or with at least one unsubstituted C1.4 alkyl group, for instance at least one methyl group. For instance, Lsmay be substituted with both a cyano group and an unsubstituted C1-4 alkyl group, or with two unsubstituted C1.4 alkyl groups. Lsmay for instance be substituted with both a cyano group and a methyl group. Lsmay for instance be a C2-4 alkylene group substituted with both a cyano group and a methyl group. Lsmay for instance be a -CH2-CH2-C(CH3)(CN)- group. Alternatively, Lsmay be substituted with two methyl groups. Lsmay for instance be a dimethyl methylene group, i.e. -C(CH3)2-.Often, each of Ruand RTis independently an unsubstituted or substituted group selected from Ci-6 alkyl and aryl. For instance, each of Ruand RTmay be independently selected from unsubstituted or substituted Ci-6 alkyl and phenyl. Often, each of Ruand RTis independently selected from unsubstituted Ci-6 alkyl and phenyl. For instance, often Ruis phenyl and RTis unsubstituted Ci-6 alkyl. For instance, Rumay be phenyl and RTmay be methyl, ethyl or propyl. Alternatively, Ruand RTmay both be unsubstituted Ci-6 alkyl, for instance they may both be methyl, ethyl or propyl, or for instance they may both be ethyl.

[0282] • RAFT moiety (ix):

[0283] >

[0284]

[0285] wherein:

[0286] LRis unsubstituted or substituted C1-20 alkylene, which C1-20 alkylene is optionally interrupted by O, OC(O) or N(R”)C(O) wherein R” is H, C1-6 alkyl or aryl; and

[0287] Ar3is an unsubstituted or substituted group selected from aryl and heteroaryl.

[0288] LRis often unsubstituted or substituted CMO alkylene, for instance unsubstituted or substituted C1-6 alkylene, or unsubstituted or substituted C1-4 alkylene. Typically, when LRis substituted, it is substituted with a cyano group (CN) and / or with at least one unsubstituted C1.4 alkyl group, for instance at least one methyl group. For instance, LRmay be substituted with both a cyano group and an unsubstituted C1-4 alkyl group, or with two unsubstituted C1.4 alkyl groups. LRmay for instance be substituted with both a cyano group and a methyl group. LRmay for instance be substituted with two methyl groups. LRmay for instance be a dimethyl methylene group, i.e. -C(CH3)2-. Often, however, LRis unsubstituted. LRis often unsubstituted C1-6 alkylene, for instance unsubstituted C1.4 alkylene, or unsubstituted C1-3 alkylene. For instance, LRmay methylene. LRis often uninterrupted. However, LRmay be interrupted by O, for instance, or by OC(O) or N(R”)C(O) wherein R” is H, C1-6 alkyl or aryl.

[0289] Ar3may be an unsubstituted or substituted aryl group, for instance unsubstituted or substituted phenyl. Ar3is often an unsubstituted group selected from aryl and heteroaryl. Ar3is often an unsubstituted aryl group, for instance unsubstituted phenyl.

[0290] • RAFT moiety (x):

[0291]

[0292] wherein:

[0293] Z is -CH2O-, -CH2N(RV)-, O or N(RV) wherein Rvis hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;Lsis unsubstituted or substituted C1-20 alkylene; and

[0294] Ar3is an unsubstituted or substituted group selected from aryl and heteroaryl.

[0295] Often, Z is N(RV). In other embodiments, however, Z may be O. Often, Z is -CH2O-.

[0296] Rvis typically hydrogen or an unsubstituted group selected from C O alkyl, aryl and heteroaryl. Rvis typically hydrogen or an unsubstituted C1-6 alkyl group, for instance H or unsubstituted C1.4 alkyl. Rvis often H, methyl or ethyl. Most typically, Rvis H.

[0297] Lsis often unsubstituted or substituted CMO alkylene, for instance unsubstituted or substituted C1-6 alkylene, or unsubstituted or substituted C1-4 alkylene. Typically, when Lsis substituted, it is substituted with a cyano group (CN) and / or with at least one unsubstituted C1.4 alkyl group, for instance at least one methyl group. For instance, Lsmay be substituted with both a cyano group and an unsubstituted C1-4 alkyl group, or with two unsubstituted C1.4 alkyl groups. Lsmay for instance be substituted with both a cyano group and a methyl group. Lsmay for instance be a C2-4 alkylene group substituted with both a cyano group and a methyl group. Lsmay for instance be a -CH2-CH2-C(CH3)(CN)- group. Alternatively, Lsmay be substituted with two methyl groups. Lsmay for instance be a dimethyl methylene group, i.e. -C(CH3)2-.

[0298] Ar3may be an unsubstituted or substituted aryl group, for instance unsubstituted or substituted phenyl. Ar3is often an unsubstituted group selected from aryl and heteroaryl. Ar3is often an unsubstituted aryl group, for instance unsubstituted phenyl.

[0299] The groups for controlling SIRDRP may be groups which comprise a CTA or initiator (which may be an iniferter, for instance a photo iniferter) for PIMP. Thus, the groups for controlling SIRDRP may be selected from groups comprising any one of the following “PIMP moieties” (i), (ii), (iii) and (iv).

[0300] • PIMP moiety (i):

[0301]

[0302] wherein:

[0303] LRis unsubstituted or substituted C1-20 alkylene, which C1-20 alkylene is optionally interrupted by O, OC(O) or N(R”)C(O) wherein R” is H, C1-6 alkyl or aryl; and

[0304] each of Ruand RTindependently is an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl.

[0305] LRis often unsubstituted or substituted C O alkylene, for instance unsubstituted or substituted C1-6 alkylene, or unsubstituted or substituted C1-4 alkylene. Typically, when LRis substituted, it is substituted with a cyano group (CN) and / or with at least one unsubstituted C1.4 alkyl group, for instance at least one methyl group. For instance, LRmay be substituted with both a cyano group andan unsubstituted C1-4 alkyl group, or with two unsubstituted C1-4 alkyl groups. LRmay for instance be substituted with both a cyano group and a methyl group. LRmay for instance be substituted with two methyl groups. LRmay for instance be a dimethyl methylene group, i.e. -C(CHs)2-. Often, however, LRis unsubstituted. LRis often unsubstituted C1-6 alkylene, for instance unsubstituted C1.4 alkylene, or unsubstituted C1-3 alkylene. For instance, LRmay methylene. LRis often uninterrupted. However, LRmay be interrupted by O, for instance, or by OC(O) or N(R”)C(O) wherein R” is H, C1-6 alkyl or aryl.

[0306] Often, each of Ruand RTis independently an unsubstituted or substituted group selected from C1-6 alkyl and aryl. For instance, each of Ruand RTmay be independently selected from unsubstituted or substituted C1-6 alkyl and phenyl. Often, each of Ruand RTis independently selected from unsubstituted C1-6 alkyl and phenyl. For instance, often Ruis phenyl and RTis unsubstituted C1-6 alkyl. For instance, Rumay be phenyl and RTmay be methyl, ethyl or propyl. Alternatively, Ruand RTmay both be unsubstituted C1-6 alkyl, for instance they may both be methyl, ethyl or propyl, or for instance they may both be ethyl.

[0307] • PIMP moiety (ii):

[0308]

[0309] wherein:

[0310] Z is -CH2O-, -CH2N(RV)-, O or N(RV) wherein Rvis hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;

[0311] Lsis unsubstituted or substituted C1-20 alkylene; and

[0312] each of Ruand RTindependently is an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl.

[0313] Often, Z is N(RV). In other embodiments, however, Z may be O. Often, Z is -CH2O-.

[0314] Rvis typically hydrogen or an unsubstituted group selected from CMO alkyl, aryl and heteroaryl. Rvis typically hydrogen or an unsubstituted C1-6 alkyl group, for instance H or unsubstituted C1.4 alkyl. Rvis often H, methyl or ethyl. Most typically, Rvis H.

[0315] Lsis often unsubstituted or substituted CMO alkylene, for instance unsubstituted or substituted C1-6 alkylene, or unsubstituted or substituted C1-4 alkylene. Typically, when Lsis substituted, it is substituted with a cyano group (CN) and / or with at least one unsubstituted C1.4 alkyl group, for instance at least one methyl group. For instance, Lsmay be substituted with both a cyano group and an unsubstituted C1-4 alkyl group, or with two unsubstituted C1.4 alkyl groups. Lsmay for instance be substituted with both a cyano group and a methyl group. Lsmay for instance be a C2-4 alkylene group substituted with both a cyano group and a methyl group. Lsmay for instance be a -CH2-CH2-C(CHs)(CN)- group. Alternatively, Lsmay be substituted with two methyl groups. Lsmay for instance be a dimethyl methylene group, i.e. -C(CHs)2-.

[0316] Often, each of Ruand RTis independently an unsubstituted or substituted group selected from Ci-6 alkyl and aryl. For instance, each of Ruand RTmay be independently selected from unsubstituted or substituted Ci-6 alkyl and phenyl. Often, each of Ruand RTis independently selected from unsubstituted Ci-6 alkyl and phenyl. For instance, often Ruis phenyl and RTis unsubstituted Ci-6 alkyl. For instance, Rumay be phenyl and RTmay be methyl, ethyl or propyl. Alternatively, Ruand RTmay both be unsubstituted Ci-6 alkyl, for instance they may both be methyl, ethyl or propyl, or for instance they may both be ethyl.

[0317] • PIMP moieties (iii) and (iv):

[0318]

[0319] wherein:

[0320] each of R15and R16independently is hydrogen or an unsubstituted or substituted group selected from Cnio alkyl, aryl and heteroaryl; and

[0321] each of R17and R18independently is an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl.

[0322] Often, each of R15and R16is independently selected from H and an unsubstituted or substituted group selected from Ci-6 alkyl and aryl. Typically, R15and R16are independently selected from H and unsubstituted or substituted Ci-6 alkyl. More typically, R15and R16are independently selected from H and unsubstituted Ci-6 alkyl. Often, R15and R16are independently selected from H and methyl. Typically, R15and R16are both H.

[0323] Often, each of R17and R18is independently an unsubstituted or substituted group selected from Ci-6 alkyl and aryl. For instance, each of R17and R18may be independently selected from unsubstituted or substituted Ci-6 alkyl and phenyl. Often, R17and R18are independently selected from unsubstituted Ci-6 alkyl and phenyl. Usually, R17and R18are both unsubstituted Ci-6 alkyl, for instance they may both be methyl, ethyl or propyl. Often, R17is ethyl and R18is ethyl.

[0324] The groups for controlling SIRDRP may for instance be groups which comprise an initiator for ATRP, and the groups which comprise an initiator for ATRP may be selected from groups which comprise any one of the following moieties:

[0325]

[0326] The groups for controlling SIRDRP may for instance be groups which comprise an initiator for ATRP, and the groups which comprise an initiator for ATRP may be selected from groups which comprise any one of the above moieties and groups which comprise any one of the following moieties:

[0327]

[0328] Alternatively, the groups for controlling SIRDRP may be groups which comprise a CTA or initiator for RAFT polymerisation, selected from groups which comprise any one of the following moieties:

[0329]

[0330]

[0331] The groups for controlling SIRDRP may be groups which comprise an initiator for photoiniferter-mediated polymerisation (PIMP), selected from groups which comprise any one of the following moieties:

[0332]

[0333] Alternatively, the groups in the polymer of the invention for controlling SIRDRP may be groups which comprise an initiator for Cu-based RDRP and / or groups which comprise a CTA for Cu-based RDRP. Any of the ATRP moieties (i), (ii), (iii), (iv), (v) and (vi) above may be employed for this purpose, or any of the groups which comprise an initiator for ATRP defined above.

[0334] The polymer of the invention for treating a surface typically comprises a polymer backbone. Generally, the reactive intermediate precursor groups are covalently-bonded reactive intermediate precursor groups. In other words, the reactive intermediate precursor groups are part of the covalently-bonded molecular structure of the polymer. Hence, the polymer comprises said reactive intermediate precursor groups. The reactive intermediate precursor groups may be within the polymer backbone or may be covalently bonded to the polymer backbone.

[0335] Often, the polymer of the invention for treating a surface comprises a polymer backbone and said reactive intermediate precursor groups covalently bonded to the polymer backbone.

[0336] The backbone of the polymer may be a hydrocarbon backbone, for instance a hydrocarbon chain, such as an alkylene chain, or for instance poly (styrene). Alternatively, it may for instance be polyethylenimine (PEI), such as branched PEI or hyperbranched PEI. The backbone may comprise more than one type of repeat unit. It may for instance be a copolymer backbone. Thus, the polymer backbone may be a homo-polymer or a copolymer. Often the polymer backbone is one that comprises aryl or heteroaryl rings, since the reactive intermediate precursor groups as defined herein may easily be attached to such rings. Typically, said aryl or heteroaryl rings are aryl rings. Usually, said aryl rings are phenyl rings. Examples of polymers that comprise aryl rings that are suitable for the polymer backbone include, for instance, polystyrene, a copolymer comprising polystyrene, a thermoplastic elastomer, polyisoprene, a copolymer comprising polyisoprene, SBS rubber, SIS rubberor poly(styrene)-poly(ethylene / butylene)-poly(styrene) (SEBS). Other examples of polymers that may be employed as the backbone of the polymer of the invention for treating a surface, include condensation polymers and addition polymers. For instance, polysaccharides, including but not limited to chitin, guar gums, gum arabic, galactomannans, or for instance locust bean gum (LBG), may be employed as the backbone. Proteins, including but not limited to Keratin, may be employed as the backbone. Polyesters, including but not limited to Nylon, polyethylene terephthalate (PET), polyoxyethylene terephthalate (POET) or a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate (PET-POET), may be employed as the backbone. Polyethers, including but not limited to polypropylene glycol (PPG), polyethylene glycol (PEG), Polyethylene oxide (PEO), may be employed as the backbone. Polyolefins, including but not limited to polyethylene (PE), polypropylene (PP), and co-polymers thereof may be employed as the backbone. Polyolefin copolymers, may be employed as the backbone. Polyacrylates and polymethacrylates, including but not limited to polyacric acid (PAA) polymethacrylic acid (PMAA), Poly2 -dimethylamino methacrylate (PDMAEMA), Poly-2 -hydroxyethyl methacylate (PHEMA), acrylonitrile, may be employed as the backbone. Polystyrene may be employed as the backbone. Thermoplatic elastomers, including but not limited to, Polybutadiene, Polyisoprene, SBS rubber and SIS rubber, may be employed as the backbone. Polycarbonates may be employed as the backbone. Polyetheretherketone (PEEK) may be employed as the backbone. Poly etherimides may be employed as the backbone. Polyimides may be employed as the backbone. Polysulfones may be employed as the backbone. Poly vinyl chloride (PVC) may be employed as the backbone. Polysilanes, Polysiloxanes, and Polyureas may be employed as the backbone. Polyurethanes may be employed as the backbone. Polylactic acid may be employed as the backbone. Polyvinylidene chloride may be employed as the backbone. Fluoropolymers, including but not limited to PTFE (polytetrafluoroethylene), PFA (perfluoroalkoxy polymer resin), fluorinated ethylene -propylene and PVDF (Kynar) may be employed as the backbone.

[0337] Polyethylene imines, for instance branched polyethyleneimine, or hyper branched polyethyleneimine may be employed as the backbone.

[0338] The reactive intermediate precursor groups groups may be bonded directly to the backbone of the polymer or, for instance, via a side chain or linker. The side chain or linker may be as defined herein for any other linker. The side chain or linker may, for instance, be an alkylene group, such as Ci-io alkylene, or an arylene group, for instance phenylene, or a heteroarylene group, or a plurality of such groups bonded together, or it may for instance be a linker group of formula (XII) as defined herein.

[0339] Typically, the polymer backbone and any linking group are at least hydrolytically stable, and they are also preferably stable to acidic and basic conditions, preferably stable to harsh conditions such as strong acid or strong base.Additionally, or alternatively, the reactive intermediate precursor groups may be within the polymer backbone itself, i.e. part of the backbone. Thus, the reactive intermediate precursor groups may be covalently bonded in between other atoms or groups that, together with the reactive intermediate precursor groups, form the polymer backbone.

[0340] Each reactive intermediate precursor group may, for instance, be within a polyimide polymer backbone, bonded to two phenyl rings within two different phthalimide units in the polyimide polymer backbone. Thus, the reactive intermediate precursor groups may be within a polyimide polymer backbone comprising repeat units of formula (X) below, as described in the applicant’s own earlier PCT application no. PCT / EP2024 / 087326, fded on 19 December 2024, the contents of which are incorporated herein by reference:

[0341]

[0342] wherein each E is a carbene precursor group selected from a hydrazone group of formula (A), a diazo group of formula (B), and a diazirine group of formula (C); and each Lxis a spacer group.

[0343] When such a polymer backbone is employed in the present invention, each group for controlling SIRDRP may for example be within, or covalently bonded to, a spacer group Lxin the polymer. Thus, Lxin said repeat unit may be substituted with a group for controlling SIRDRP as defined herein. Such polyimide polymers comprising repeat units of formula (X) may be produced by reacting a diamino compound H2N-LX-NH2 (wherein Lxis said spacer group) with one or more carbonyl bis(phthalic anhydride) compounds, and then converting the central carbonyl group in each of the repeat units of formula into a carbene precursor group E, selected from a hydrazone group of formula (A), a diazo group of formula (B), and a diazirine group of formula (C), as described in PCT application no. PCT / EP2024 / 087326, filed 19 December 2024. In the present invention the spacer group Lxmay be modified to include a group for controlling SIRDRP as defined herein.

[0344] Thus, the polymer may comprise a polymer backbone, and the reactive intermediate precursor groups may be within the polymer backbone or may be covalently bonded to the polymer backbone.

[0345] Typically, the reactive intermediate precursor groups are covalently bonded to the polymer backbone.

[0346] Usually, when the reactive intermediate precursor groups are covalently bonded to the polymer backbone, each group for controlling SIRDRP is covalently bonded to one of those reactive intermediate precursor groups. Thus, each group for controlling SIRDRP may be covalently bonded to (a different) one of the reactive intermediate precursor groups. Thus, often, each of the reactiveintermediate precursor groups is covalently bonded to the polymer backbone, and each of the groups for controlling SIRDRP is in turn covalently bonded to a said reactive intermediate precursor group.

[0347] Alternatively, when the reactive intermediate precursor groups are covalently bonded to the polymer backbone, each group for controlling SIRDRP may also be covalently bonded to the polymer backbone, but at a different point of the polymer backbone from the points at which the reactive intermediate precursor groups are bonded to the polymer backbone. In other words, each group for controlling SIRDRP may be covalently bonded to a different atom within the polymer backbone from the atoms to which the reactive intermediate precursor groups are covalently bonded.

[0348] Polymers in which reactive intermediate precursor groups are covalently bonded to a polymer backbone may be of formula (II)

[0349]

[0350] wherein:

[0351] Q is a polymer (forming the polymer backbone);

[0352] n is said integer equal to or greater than 3;

[0353] each L, which is the same or different, is a single bond or a linker group;

[0354] each R, which is the same or different, is a terminal group; and

[0355] each E, which is the same or different, is one of said reactive intermediate precursor groups, wherein: x is 1 and E is a carbene precursor group independently selected from a hydrazone group of formula (A), a diazo group of formula (B) and a diazirine group of formula (C), or x is 0 and E is a nitrene precursor group which is an azide group of formula (D):

[0356]

[0357] wherein R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-6 alkyl group or an unsubstituted or substituted aryl group.

[0358] Such polymers of formula (II) in which each R is a terminal group and their synthesis methods are disclosed in the applicant’s own earlier PCT application no. PCT / EP2024 / 087326, fded on 19 December 2024, and in its priority document GB2319515.9, and also in WO 2010 / 100410 Al and WO 2010 / 100413 A2, and in their priority documents GB 0903563.5 and GB 0914692.9. The entire contents of each of PCT / EP2024 / 087326, WO 2010 / 100410 Al, WO 2010 / 100413 A2, and their priority applications GB2319515.9, GB 0903563.5 and GB 0914692.9, are hereby incorporated herein by reference.Such polymers of formula (II) can be modified to incorporate the groups for controlling SIRDRP of the present invention. This may be achieved by, instead of employing R groups which are terminal groups, the R groups (or at least some of the R groups if not all of the R groups) are groups which comprise a group for controlling SIRDRP. Alternatively, such polymers can be modified to incorporate the groups for controlling SIRDRP by ensuring that groups for controlling SIRDRP are bonded to, or incorporated within, the polymer backbone Q.

[0359] Thus, the polymer of the invention for treating a surface may be a polymer of formula (II)

[0360]

[0361] wherein:

[0362] Q is a polymer;

[0363] n is said integer equal to or greater than 3;

[0364] each L, which is the same or different, is a single bond or a linker group;

[0365] each R, which is the same or different, is a terminal group or a group comprising at least one of said groups for controlling SIRDRP; and

[0366] each E, which is the same or different, is one of said reactive intermediate precursor groups, wherein: x is 1 and E is a carbene precursor group independently selected from a hydrazone group of formula (A), a diazo group of formula (B) and a diazirine group of formula (C), or x is 0 and E is a nitrene precursor group which is an azide group of formula (D):

[0367]

[0368] wherein R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-6 alkyl group or an unsubstituted or substituted aryl group,

[0369] provided that each of said groups for controlling SIRDRP is independently either (i) bonded to said polymer Q, or (ii) within a said group R which is a group comprising at least one of said groups for controlling SIRDRP. Often, each of said groups for controlling SIRDRP is within a said group R which is a group comprising at least one of said groups for controlling SIRDRP.

[0370] Thus, typically, each R is a group comprising at least one of said groups for controlling SIRDRP.

[0371] Alternatively, however, the polymer Q may comprise the groups for controlling SIRDRP. Thus, each of said groups for controlling SIRDRP may be bonded to Q. Usually, in these cases, each R is a terminal group.When the polymer of the invention for treating a surface of formula (II) does comprise terminal groups, R, the nature of the terminal groups is not critical. However, the reactivity of the polymer of the invention and its derived reactive intermediate (e.g. carbene reactive intermediate) can be modified by including electron releasing or electron withdrawing groups within the terminal group R. In addition, the solubility of the polymer of the invention of formula (II) and its derived reactive intermediate (e.g. carbene or nitrene reactive intermediate) can be modified by including groups of a given hydrophilicity or lipophilicity within the terminal group R. When R is an aryl or heteroaryl group, the reactivity of the compound and its derived reactive intermediate can be modified by including electron releasing or electron withdrawing groups on the aromatic ring. In addition, the solubility of the compound and its derived reactive intermediate can be modified by including groups of a given hydrophilicity or lipophilicity on the aromatic ring.

[0372] Accordingly, in the polymer of the invention of formula (II), when R is a terminal group, each terminal group R, which may be the same or different, is typically selected from hydrogen, aryl, heteroaryl, C1-20 perfluoroalkyl, Ci-w alkoxy, aryloxy, di(Ci-io)alkylamino, alkylarylamino, diarylamino, Ci-w alkylthio, arylthio and CR’s, wherein each R’ is independently selected from a halogen atom, C1-20 haloalkyl, C1-20 fluoroalkyl, C1-20 perfluoroalkyl, aryl, heteroaryl, C3-20 carbocyclyl, C3-20 heterocyclyl, tri(Ci-2o alkyl)silyl, aryldi(Ci-2o alkyl)silyl, diaryl(Ci-2o alkyl)silyl, triarylsilyl, C2-20 alkenyl, C2-20 alkynyl and C1-20 alkyl, which C1-20 alkyl and C1-20 perfluoroalkyl are optionally interrupted by N(R”), O, S or arylene wherein R” is H, C1-6 alkyl or aryl;

[0373] provided that when R is aryl or heteroaryl said aryl or heteroaryl may be unsubstituted or substituted by one, two, three, four or five groups (more typically, one two or three groups, for instance one or two groups, or one group), which groups are the same or different and typically are independently selected from C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C1-20 haloalkyl, C1-20 fluoroalkyl, C1-20 perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, CMO alkylamino, di(Ci. io)alkylamino, arylamino, diarylamino, arylalkylamino, amido, acyl, acyloxy, acylamido, ester, CMO alkoxy, aryloxy, haloalkyl, thiol, CMO alkylthio, arylthio, sulfonic acid, sulfonyl, sulfonamide, tri(Ci-2o alkyl)silyl, aryldi(Ci-2o alkyl)silyl, diaryl(Ci-2o alkyl)silyl and triarylsilyl.

[0374] More typically, in formula (II), when R is a terminal group, each terminal group R, which is the same or different, is aryl or heteroaryl, which aryl or heteroaryl is unsubstituted or substituted by one, two, three, four or five groups (more typically, one two or three groups, for instance one or two groups, or one group), which groups are the same or different and typically are independently selected from C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C1-20 haloalkyl, C1-20 fluoroalkyl, C1-20 perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C O alkylamino, di(Ci-io)alkylamino, arylamino, diarylamino, arylalkylamino, amido, acyl, acyloxy, acylamido, ester, CMO alkoxy, aryloxy, haloalkyl, thiol, CMO alkylthio, arylthio, sulfonic acid, sulfonyl, sulfonamide, tri(Ci-2o alkyl)silyl, aryldi(Ci-2o alkyl)silyl, diaryl(Ci-2o alkyl)silyl and triarylsilyl.Often, in formula (II), when R is a terminal group, each terminal group R, which is the same or different, is phenyl which is unsubstituted or substituted by one, two, three, four or five groups (more typically, one two or three groups, for instance one or two groups, or one group), which groups are the same or different and typically are independently selected from C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C1-20 haloalkyl, C1-20 fluoroalkyl, C1-20 perfluoroalkyl, aryl, cyano, nitro, hydroxy, halo, carboxy, amino, C1-10 alkylamino, di(Ci-io)alkylamino, arylamino, diarylamino, arylalkylamino, amido, acyl, acyloxy, acylamido, ester, C1-10 alkoxy, aryloxy, haloalkyl, thiol, C1-10 alkylthio, arylthio, sulfonic acid, sulfonyl, sulfonamide, tri(Ci-2o alkyl)silyl, aryldi(Ci-2o alkyl)silyl, diaryl(Ci-2o alkyl)silyl and triarylsilyl.

[0375] However, as mentioned above, it is often the case that each R, in the polymer of the invention for treating a surface of formula (II), is a group comprising at least one of said groups for controlling SIRDRP. When this is the case, each R, which is the same or different, may comprise any of the groups for controlling SIRDRP described herein.

[0376] Thus, the polymer of the invention for treating a surface may be of formula (II) as defined above. Such a polymer comprises n groups of the following formula, which are bonded to the polymer Q (which may also be referred to herein as the polymer backbone Q) :

[0377]

[0378] and therefore it comprises n reactive intermediate precursor groups, E, wherein n is an integer equal to or greater than 3. The n reactive intermediate precursor groups, E, are the same or different, i.e. they may differ from one (R)x-E-L- group to the next. Similarly, the linker groups (or single bonds) L, the integer x and / or the terminal groups R, when present, may differ from one (R)x-E-L- group to the next in the polymer for treating a surface of formula (II). For instance, the polymer for treating a surface of formula (II) may comprise a first group of formula (R)x-E-L-, a second group of formula (R)x-E-L-, and a third group of formula (R)x-E-L-, wherein the reactive intermediate precursor groups, E, the linker groups (or single bonds) L, the integer x and / or the groups R are different in each of the first, second and third (R)x-E-L- groups. Typically, however, E is the same reactive intermediate precursor group in all of the (R)x-E-L- groups in the polymer for treating a surface of formula (II). Similarly, L is typically the same in all of the (R)x-E-L- groups in the polymer for treating a surface of formula (II). Similarly, R is typically the same group in all of the (R)x-E-L- groups in the compound of formula (II), and / or x is the same integer in all of those groups.

[0379] The number of (R)x-E-L- groups (and hence the number of reactive intermediate precursor groups E) in the polymer for treating a surface of formula (II), n, is an integer equal to or greater than 3. The integer n may be as further defined above.

[0380] As discussed above, each E may be a carbene precursor group independently selected from a hydrazone group of formula (A), a diazo group of formula (B) and a diazirine group of formula (C), inwhich case x is 1, or a nitrene precursor group which is an azide group of formula (D), in which case x is 0. Thus, the n (at least 3) (R)x-E-L- groups in formula (II) may be independently selected from groups of the following formulae (A’), (B’), (C’) and (D’):

[0381]

[0382] wherein R, L and R1are as defined above for the compound of formula (II).

[0383] The n reactive intermediate precursor groups employed in the polymer for treating a surface of formula (II) may be nitrene precursor groups, i.e. azide groups of formula (D). Thus, each E may be an azide group of formula (D), in which case x is 0, and each (R)x-E-L- group in formula (II) is a group of the formula (D’)

[0384]

[0385] wherein L is as defined above for the polymer for treating a surface of formula (II).

[0386] In this case, when E is an azide group of formula (D), x is 0, and therefore when the R groups are absent, Q comprises the groups for controlling SIRDRP. In other words, when E is an azide group of formula (D) and therefore x is 0, the polymer Q (which forms the backbone of the polymer of the invention for treating a surface) comprises the groups for controlling SIRDRP.

[0387] Thus, typically, when E is an azide group of formula (D) and x is 0, each of said groups for controlling SIRDRP is bonded to Q.

[0388] More typically, however, the n reactive intermediate precursor groups employed in the polymer of the invention of formula (II) are carbene precursor groups. Thus, each E may be selected from hydrazone groups of formula (A), a diazo group of formula (B) and a diazirine group of formula (C), in which case x is 1 and each (R)x-E-L- group in formula (II) is a group of the formula (A’), (B’) or (C’)

[0389]

[0390] wherein R, L and R1are as defined above for the polymer of the invention of formula (II).Each E may for instance be selected from hydrazone groups of formula (A) and a diazo group of formula (B), in which case x is 1 and each (R)x-E-L- group in formula (II) is a group of the formula (A’) or (B’)

[0391]

[0392] wherein R, L and R1are as defined herein for the polymer of the invention of formula (II).

[0393] Thus, often, the polymer of the invention of formula (II) is a compound of formula (A”) or a compound of formula (B”)

[0394]

[0395] wherein n, R, L, R1and Q are as defined herein for the polymer of the invention of formula (II).

[0396] More typically, however, each E is selected from hydrazone groups of formula (A), in which case x is 1 and each (R)x-E-L- group in formula (II) is a group of the formula (A’)

[0397]

[0398] <

[0399] wherein R, L and R1are as defined herein for the polymer of the invention of formula (II).

[0400] Thus, the polymer of the invention of formula (II) is more typically a compound of formula (A”)

[0401]

[0402] wherein n, R, L, R1and Q are as defined herein for the polymer of the invention of formula (II).In the hydrazone groups of formula (A), (A’) and (A”) in the crosslinker compound of formula (II), R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-e alkyl group or an unsubstituted or substituted aryl group.

[0403] Often, R1is H. However, hydrazone groups of formula (A) in which R1is -S(O)2R2are often preferred. Typically, R2is an unsubstituted or substituted Ci-6 alkyl group, an unsubstituted or substituted phenyl group, or an unsubstituted or substituted naphthyl group. Often, R2is Ci-6 alkyl, phenyl or naphthyl, which phenyl or naphthyl is unsubstituted or substituted with Ci-6 alkyl, di(Ci-e alkyl)amino, hydroxyl, nitro, cyano or methoxy. More typically, R2is Ci-6 alkyl, phenyl or naphthyl, which phenyl or naphthyl is unsubstituted or substituted with Ci-6 alkyl or di(Ci-e alkyl)amino.

[0404] Typically, R1is -S(O)2R2wherein R2is phenyl substituted with Ci-6 alkyl. More typically, R1is -S(O)2R2wherein R2is phenyl substituted with methyl (i.e. tolyl). Thus, often, R1is a tosyl group. In another embodiment, R1is H.

[0405] The nature of the groups L in the polymer of the invention for treating a surface is also not critical. Any suitable linking group may be employed or L may be a single bond.

[0406] Typically, however, each L, which is the same or different, is a single bond or a group of formula (XII)

[0407] -A1-«2-A3—(xn)

[0408] wherein:

[0409] A1is bonded to E, wherein, when E is a carbene precursor group and x is 1, A1is bonded to the carbon atom bonded to R, and when E is a nitrene precursor group and x is 0, A1is bonded to an azide group of formula (D), wherein A1is:

[0410] a single bond or an unsubstituted or substituted group selected from arylene, heteroarylene, Ci-20 perfluoroalkylene, *-0-Ci-2o alkylene, *-0-Ci-2o perfluoroalkylene, *-O-arylene, *-O-heteroarylene, *-N(R”)-CI-2O alkylene, *-N(R”)-CI-2O perfluoroalkylene, *-N(R”)-arylene, *-N(R”)-heteroarylene, *-S-Ci-2o alkylene, *-S-Ci-2o perfluoroalkylene, *-S-arylene, *-S-heteroarylene, *-C(R’)2-CI-2O alkylene, *-C(R’)2-CI-2O perfluoroalkylene, *-C(R’)2-arylene, *-C(R’)2-heteroarylene and Ci-20 alkylene, wherein each R’ is independently selected from a halogen atom, Cnio haloalkyl, Cnio fluoroalkyl, Cnio perfluoroalkyl, aryl, heteroaryl, C3-10 carbocyclyl, Cs-ioheterocyclyl, tri(Cnio alkyl)silyl, aryldi(Cnio alkyl)silyl, diaryl(Cnio alkyl)silyl, triarylsilyl, C2-10 alkenyl, C2-10 alkynyl and Cnio alkyl, wherein * is the point of attachment of A1to E, wherein each of said C1-20 alkylene and C1-20 perfluoroalkylene groups is optionally interrupted by N(R”), O, S or arylene, and wherein R” is independently selected from H, Cne alkyl and aryl;

[0411] A2is a single bond or an unsubstituted or substituted group selected from C1-20 alkylene, C1-20 perfluoroalkylene, arylene, heteroarylene, * -C1-20 alkylene-(0-Ci-2o alkylene-)mwherein m is 1 to 20, *-Z1-Ci-2o alkylene, *-Z1-Ci-2o perfluoroalkylene, *-Z’-arylene, *-Z’ -heteroarylene and *-Z1-Ci-2o alkylene-(0-Ci-2o alkylene-)mwherein m is 1 to 20, wherein Z1is selected from O, S, C(O), S(O),S(0)2, N(R”), C(0)0, 0C(0), C(O)N(R”) and N(R”)C(O), wherein * is the point of attachment of A2to A1, wherein each of said C1-20 alkylene and C1-20 perfluoroalkylene groups is optionally interrupted by N(R”), O, S or arylene, and wherein each R” is independently selected from H, Ci-e alkyl and aryl; and

[0412] A3is a single bond or an unsubstituted or substituted group selected from *-Z2-arylene, *-Z2-heteroarylene, *-Z2-CI-2O alkylene, arylene, heteroarylene, C1-20 alkylene, *-Z2-arylene-O, *-Z2-heteroarylene-O, *-Z2-CI-2O alkylene-O, *-arylene-O, *-heteroarylene-O, *-Ci-2o alkylene-O, C(O), S(O)2, *-OC(O), *-N(R”)C(O), O, S, N(R”), *-C(O)O, *-C(O)N(R”), *-S(O)2O, C120 alkenylene, Ci.

[0413] 20 alkynylene, *-Z2-CI-2O alkenylene and *-Z2-CI-2O alkynylene, wherein Z2is selected from O, S, N(R”), C(O), S(O), S(O)2, C(O)O, OC(O), C(O)N(R”) and N(R”)C(O), wherein each R” is independently selected from H, Ci-e alkyl and aryl, and wherein * is the point of attachment of A3to A2.

[0414] Typically, at least one of A1, A2and A3is not a single bond. In particular, A1is typically not a single bond. Often, A1is an unsubstituted or substituted group selected from arylene and heteroarylene. Typically, A1is an unsubstituted or substituted arylene group. More typically, A1is an unsubstituted or substituted phenylene group, even more typically an unsubstituted phenylene group.

[0415] In another embodiment, however A1is a single bond.

[0416] Usually, A2is an unsubstituted or substituted group selected from C1-20 alkylene, C1-20 perfluoroalkylene, *-Ci-2o alkylene-(0-Ci-2o alkylene-)mwherein m is 1 to 20, *-Z1-Ci-2o alkylene, *-Z’-Ci^o perfluoroalkylene and *-Z1-Ci-2o alkylene-(0-Ci-2o alkylene-)mwherein m is 1 to 20, wherein Z1is selected from O, S, C(O), S(O), S(O)2, N(R”), C(O)O, OC(O), C(O)N(R”) and N(R”)C(O), wherein * is the point of attachment of A2to A1, wherein each of said C1-20 alkylene and C1-20 perfluoroalkylene groups is optionally interrupted by N(R”), O, S or arylene, and wherein each R” is independently selected from H, C1-6 alkyl and aryl. More typically, A2is C1-10 alkylene or *-Ci-6 alkylene-(O-C2-4 alkylene-)mwherein m is 1 to 20 and wherein * is the point of attachment of A2to A1.

[0417] In one embodiment, A1is a phenylene group, typically an unsubstituted phenylene group, and A2is Ci-10 alkylene or *-Ci-6 alkylene-(O-C2-4 alkylene-)mwherein m is 1 to 20 and wherein * is the point of attachment of A2to A1.

[0418] Typically, A3is a single bond, O, C(O), *-OC(O) or an unsubstituted or substituted group selected from *-Z2-arylene, *-Z2-heteroarylene, arylene, heteroarylene, * -Z2-arylene-O, *-Z2-heteroarylene-O, *-arylene-0 and *-heteroarylene-O, wherein Z2is selected from O, S, N(R”), C(O), S(O), S(O)2, C(O)O, OC(O), C(O)N(R”) and N(R”)C(O), wherein each R” is independently selected from H, C1-6 alkyl and aryl, and wherein * is the point of attachment of A3to A2.

[0419] More typically, A3is a single bond, O, C(O), *-OC(O) or an unsubstituted or substituted group selected from *-O-arylene, *-O-heteroarylene, *-0-arylene-0 and *-O-heteroarylene-Owherein * is the point of attachment of A3to A2. Even more typically, A3is a single bond, O, or an unsubstituted or substituted group selected from *-O-arylene, *-O-heteroarylene, *-0-arylene-0 and *-O-heteroarylene-O wherein * is the point of attachment of A3to A2. Even more typically, A3is a single bond, O, or an unsubstituted or substituted group selected from * -O-heteroarylene and * -O-heteroarylene-0 wherein * is the point of attachment of A3to A2.

[0420] In one embodiment A1, A2and A3are all single bonds, which means that L is itself a single bond. Thus, in some embodiments, L is a single bond and each of the reactive intermediate precursor functionalities, E, is bonded directly to Q.

[0421] For instance in some embodiments, wherein the polymer of the invention for treating a surface comprises hydrazone groups of formula (A) in which R1is -S(O)2R2(i.e. sulfonylhydrazone groups), L may be a single bond. In such embodiments, the carbon atoms of the carbene precursor groups (which carbon atoms are bonded to R) are bonded directly to Q.

[0422] Q is a polymer, which may be referred to as the “backbone” of the polymer of the invention for treating a surface, of formula (II). The polymer Q - i.e. the backbone - is functionalised with said n groups of formula (R)x-E-L- in said polymer of the invention of formula (II). As is shown in formula (II), each of the n reactive intermediate precursor groups E is bonded to the polymer Q via the group L, which may be a linking group or a single bond. When L is a group of formula (XII) as defined above, each of the n reactive intermediate precursor groups is typically bonded to the polymer Q via group A3of said group of formula (XII).

[0423] Synthesis methods for coupling reactive intermediate precursor groups (or carbonyl precursors thereto) to a polymer Q (which may be referred to herein as a polymer backbone, Q) are described in detail in WO 2010 / 100410 Al, and in the priority documents of WO 2010 / 100410 Al, GB 0903563.5 and GB 0914692.9, whereby the reactive intermediate precursor groups (or carbonyl precursors thereto) are coupled to a polymer Q’ by reaction between a functional group on the linker moiety of the reactive intermediate precursor group (or on the carbonyl precursor thereto) with functional groups, -A4-X2on Q’. Thus, the polymer Q of the compound of formula (II) is typically attached to the groups L of the n reactive intermediate precursor groups via n linker groups of formula A4.

[0424] Accordingly, Q in the polymer of the invention of of formula (II) is typically a polymer which comprises n linker groups of formula A4, each of which is attached to a group L, wherein n is an integer equal to or greater than 3. Each individual A4is the same as or different from the others and is independently selected from a single bond, -Z3-arylene-*, -Z3-heteroarylene-*, -Z3-CI-2O alkylene-*, arylene, heteroarylene, C1-20 alkylene, -Z3-arylene-O-*, -Z3-heteroarylene-O-*, -Z3-CI-2O alkylene-O-*, arylene-O-*, heteroarylene-O-*, C1.20 alkylene-O-*, -C(O)-*, S(O)2, -OC(O)-*, -N(R”)C(O)-*, O, S, N(R”), -C(O)O-*, -C(O)N(R”)-*, -S(O)2O-*, C1-20 alkenylene, C1-20 alkynylene, -Z3-CI-2O alkenylene-* and -Z3-CI-2O alkynylene-*, wherein Z3is selected from O, S, N(R”), C(O), S(O), S(O)2, C(O)O,0C(0), C(O)N(R”) and N(R”)C(O), wherein each R” is independently selected from H, CM alkyl and aryl, and wherein * is the point of attachment of A4to L.

[0425] In one embodiment, each A4is independently selected from O, arylene-O-*, heteroarylene-O-*, Ci-20 alkylene-O-*, -Z3-arylene-O-*, -Z3-heteroarylene-O-*, -Z3-CI-2O alkylene-O-*, wherein Z3is selected from O, S, N(R”), C(O), S(O), S(O)2, C(O)O, OC(O), C(O)N(R”) and N(R”)C(O), wherein each R” is independently selected from H, CM alkyl and aryl, wherein * is the point of attachment of A4to L. More typically, in this embodiment, A4is O.

[0426] In another embodiment, each A4is independently selected from a single bond, -Z3-arylene-*, -Z3-heteroarylene-*, -Z3-CI-2O alkylene-*, arylene, heteroarylene, C1-20 alkylene, -C(O)-, S(O)2, -OC(O)-*, -N(R”)C(O)-*, C1-20 alkenylene, C1-20 alkynylene, -Z3-CI-2O alkenylene-* and -Z3-CI-2O alkynylene-*, wherein Z3is selected from O, S, N(R”), C(O), S(O), S(O)2, C(O)O, OC(O), C(O)N(R”) and N(R”)C(O), wherein each R” is independently selected from H, CM alkyl and aryl, and wherein * is the point of attachment of A4to L.

[0427] In a further embodiment, A4is -C(O)-.

[0428] In another embodiment, A4is -Z3-heteroarylene-* wherein * is the point of attachment of A4to L. Typically, Z3is O. Typically, in this embodiment, A4is a group of formula (XIX)

[0429]

[0430] wherein * is the point of attachment to L and wherein XLis halo, hydroxyl, Ci-w alkoxy, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, aryl, aralkyl, cyano, amino, CMO alkylamino, di(Ci-io)alkylamino, arylamino, diarylamino, arylalkylamino, amido, acylamido, C1-20 haloalkyl, ester, acyl, acyloxy, aryloxy, nitro, carboxy, sulfonic acid, sulfonyl, sulphonamide, thiol, CMO alkylthio or arylthio.

[0431] Typically, XLis halo or hydroxyl. More typically, XLis halo, for instance chloro.

[0432] The polymer Q, also referred to herein as the backbone of the polymer of the invention, may be a linear polymer, a branched polymer or a hyperbranched polymer. The polymer may for instance be a homopolymer or a copolymer. The co-polymer may be a ter-polymer or any other multiple combination polymer. Suitable copolymers include polymethylmethacrylate-co-poly-2-dimethylamino ethyl methacrylate, for instance.

[0433] Also covered are different polymer acrhitectures, including but not limited to branched polymers; block copolymers, for instance, SBS rubber (Kraton), or EO-PO-EO (Pluronic); star polymers (Tetronic); or hyperbranced polymers (PEI).

[0434] Polymers of different molecular weight ranges are also covered, from small macromers with a repeat unit length of a dimer, to polymers with a molecular weight of millions. The degree ofpolymerisation, Dp, of the polymer (i.e. the polymer molecular weight divided by the molecular weight of the repeat unit) may be from 2 to 100,000,000.

[0435] Typically, the polymer employed is either soluble or dispersable.

[0436] In one embodiment, Q is selected from any of the polymers listed in the following paragraph and their copolymers. Thus, Q may be a homopolymer comprising any of the following polymers, or a copolymer which comprises the monomeric units of any one or more of the following polymers:

[0437] Condensation polymers and Addition polymers. Polysaccharides, including but not limited to chitin, guar gums, gum arabic, galactomannans, for instance locust bean gum (LBG). Proteins, including but not limited to Keratin. Polyesters, including but not limited to Nylon, polyethylene terephthalate (PET), polyoxyethylene terephthalate (POET) or a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate (PET-POET). Polyethers, including but not limited to polypropylene glycol (PPG), polyethylene gloycol (PEG), Polyethylene oxide (PEO). Polyolefins, including but not limited to polyethylene (PE), polypropylene (PP), and co-polymers thereof.

[0438] Polyolefin co-polymers. Polyacrylates and polymethacrylates, including but not limited to polyacric acid (PAA) polymethacrylic acid (PMAA), Poly2 -dimethylamino methacrylate (PDMAEMA), Poly-2-hydroxyethyl methacylate (PHEMA), acrylonitrile. Polystyrene. Thermoplatic elastomers, including but not limited to, Polybutadiene, Polyisoprene, SBS rubber and SIS rubber. Polycarbonates.

[0439] Polyetheretherketone (PEEK). Polyetherimides. Polyimides. Polysulfones. Poly vinyl chloride (PVC). Polysilanes. Polysiloxanes. Polyureas. Polyurethanes. Polylactic acid. Polyvinylidene chloride.

[0440] Fluoro-polymers, including but not limited to PTFE (polytetrafluoroethylene), PFA (perfluoroalkoxy polymer resin), fluorinated ethylene -propylene and PVDF (Kynar). Polyethylene imines.

[0441] Q may alternatively be be a salt of any of the polymers described herein.

[0442] Q may for instance comprise a polysaccharide, a protein, a polyester, a polyether, a polyacrylate, a polymethacrylate, a polycarbonate, polyetheretherketone (PEEK), a polyetherimide, a polyimide, a polysulfone, poly(vinyl chloride), a polysilane, a polysiloxane, a polyurea, a polyurethane, polylactic acid, polyvinylidene chloride, a fluoro-polymer, a polyethylene imine, or a salt thereof.

[0443] Typically, the polymer Q has a functionality -A4-X2as defined herein and in WO 2010 / 100410 Al, for instance an OH, NH, SH or aryl (typically phenyl) functionality that allows single step transformation to introduce the [R]x-E-L- groups containing the reactive intermediate precursor groups E (or carbonyl precursors thereof) onto the polymer.

[0444] Alternatively, however, any polymer can be modified to include the reactive intermediate precursor group using a two-step process. In such a process, an -A4-X2functionality, for instance an -OH, NH, SH or aryl (typically phenyl) functionality is first reacted onto the desired polymer.

[0445] Subsequently, that -A4-X2functionality, which has been newly-introduced on the polymer, is coupled with a further compound, which comprises the reactive intermediate precursor group of formula (I), to introduce that reactive intermediate precursor group onto the polymer.Thus, Q often comprises n linker groups of formula A4which are the same or different and are as defined above, each of which is attached to a group L of a reactive intermediate precursor group of formula (I), wherein n is an integer equal to or greater than 2.

[0446] In one embodiment, A4is O or -Z3-heteroarylene-* wherein * is the point of attachment of A4to L. Typically, Z3is O. More typically, in this embodiment, A4is O or a group of formula (XIX) as defined above.

[0447] In one embodiment, Q comprises a polysaccharide, a polyester or polystyrene.

[0448] In one embodiment, when Q comprises a polysaccharide, the polysaccharide is a chitin, guar gum, gum arabic, or a galactomannan.

[0449] In one embodiment, when Q comprises a polyester, the polyester is Nylon, polyethylene terephthalate (PET), polyoxyethylene terephthalate (POET) or a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate (PET-POET).

[0450] As mentioned above, in some embodiments of the polymer of the invention of formula (II), L may be a single bond.

[0451] Typically, when L is a single bond, Q comprises at least n aryl or heteroaryl rings, wherein each L which is single bond is attached directly to a said aryl or heteroaryl ring of Q. The single bond, L, thereby bonds the aryl or heteroaryl ring directly to the carbon atom of the carbene precursor group (i.e. the carbon atom that is also bonded to R in the crosslinker compound of formula II) or to the nitrogen atom of the nitrene precursor group (azide group). In this embodiment Q is a polymer that comprises said n aryl or heteroaryl rings. Typically, said aryl or heteroaryl rings are aryl rings.

[0452] Usually, said aryl rings are phenyl rings. Examples of polymers that comprise aryl rings include, for instance, polystyrene, a copolymer comprising polystyrene, a thermoplastic elastomer, polyisoprene, a copolymer comprising polyisoprene, SBS rubber, SIS rubber or poly( styrene) -poly (ethylene / butylene) -poly (styrene) ( SEB S) .

[0453] More typically, when L is a single bond, Q is a polymer which comprises at least n aryl or heteroaryl rings, wherein each L which is single bond is attached directly to a said aryl or heteroaryl ring, thereby bonding the aryl or heteroaryl ring directly to the carbon atom which is bonded to R. Typically, said aryl or heteroaryl rings are aryl rings. Typically, said aryl rings are phenyl rings.

[0454] Thus, in some embodiments of the polymer of the invention of formula (II), L is a single bond and Q is a polymer which comprises at least n aryl or heteroaryl rings, wherein each L which is single bond is attached directly to a said aryl or heteroaryl ring, thereby bonding the aryl or heteroaryl ring directly to the carbon atom which is bonded to R. Typically, said aryl or heteroaryl rings are aryl rings. Typically, said aryl rings are phenyl rings. Usually, in such embodiments, Q comprises polystyrene, a copolymer comprising polystyrene, a thermoplastic elastomer, polyisoprene, a copolymer comprising polyisoprene, SBS rubber, SIS rubber or poly( styrene) -poly (ethylene / butylene) -poly (styrene) ( SEB S) .Alternatively, L in the compound of formula (II) may be a group of formula (XII) as defined above, in which A3is a single bond or an unsubstituted or substituted group selected from * -Z2-arylene, *-Z2-heteroarylene, *-Z2-CI-2O alkylene, arylene, heteroarylene, C1-20 alkylene, C(O), S(O)2, *-OC(O) and *-N(R”)C(O), wherein Z2is selected from O, S, N(R”), C(O), S(O), S(O)2, C(O)O, OC(O), C(O)N(R”) and N(R”)C(O), wherein each R” is independently selected from H, Ci-e alkyl and aryl, and wherein * is the point of attachment of A3to A2.

[0455] Typically, in this embodiment, A3is a single bond.

[0456] Alternatively, A3may be an unsubstituted or substituted group selected from *-O-arylene and *-O-heteroarylene wherein * is the point of attachment of A3to A2. For instance, A3may be a group of formula (XVII)

[0457]

[0458] wherein * is the point of attachment of A3to A2, and wherein XLis halo, hydroxyl, C1-10 alkoxy, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, aryl, aralkyl, cyano, amino, C1-10 alkylamino, di(Ci-io)alkylamino, arylamino, diarylamino, arylalkylamino, amido, acylamido, C1-20 haloalkyl, ester, acyl, acyloxy, aryloxy, nitro, carboxy, sulfonic acid, sulfonyl, sulphonamide, thiol, Cn 10 alkylthio or arylthio.

[0459] Typically, XLis halo or hydroxyl. More typically, XLis halo, for instance chloro.

[0460] Typically, when A3is an unsubstituted or substituted group selected from *-O-arylene and *-O-heteroarylene, A1is unsubstituted or substituted phenylene and A2is an unsubstituted or substituted group selected from C1-20 alkylene, C1-20 perfluoroalkylene, *-Ci-2o alkylene-(0-Ci-2o alkylene-)mwherein m is 1 to 20, *-Z1-Ci-2o alkylene, *-Z1-Ci-2o perfluoroalkylene and *-Z1-Ci-2o alkylene-(O-Ci.

[0461] 20 alkylene-)mwherein m is 1 to 20, wherein Z1is selected from O, S, C(O), S(O), S(O)2, N(R”), C(O)O, OC(O), C(O)N(R”) and N(R”)C(O), wherein * is the point of attachment of A2to A1, wherein each of said C1-20 alkylene and C1-20 perfluoroalkylene groups is optionally interrupted by N(R”), O, S or arylene, and wherein each R” is independently selected from H, C1-6 alkyl and aryl. More typically, in this embodiment, A1is unsubstituted or substituted phenylene and A2is C1-10 alkylene or *-Ci-2o alkylene-(0-Ci-2o alkylene-)mwherein m is 1 to 20 and wherein * is the point of attachment of A2to A1. Even more typically A2is *-Ci-6 alkylene-(O-C2-4 alkylene-)mwherein m is 1 to 20 and wherein * is the point of attachment of A2to A1. Usually, in these embodiments, A3is a group of formula (XVII)

[0462]

[0463] wherein * is the point of attachment of A3to A2and wherein XLis as defined above. Thus, L may for instance be the following group:

[0464]

[0465] wherein * is the point of attachment of L to the carbon atom bonded to R and wherein XLis as defined above.

[0466] When A3is a single bond, A1is typically unsubstituted or substituted phenylene and A2is typically unsubstituted or substituted C1-20 alkylene, for instance unsubstituted or substituted C1-10 alkylene, unsubstituted or substituted C1.4 alkylene or CH2. Thus, L may for instance be the following group:

[0467]

[0468] wherein * is the point of attachment of L to the carbon atom bonded to R.

[0469] In another embodiment, when A3is a single bond, A1and A2are also single bonds and therefore L itself is a single bond. Typically, in this embodiment, each L is attached to a phenyl group of Q. Thus, typically, in this embodiment, Q is a polymer bearing phenyl groups, for instance polystyrene.

[0470] Typically, when L is a group of formula (XII) as defined above, in which A3is a single bond or an unsubstituted or substituted group selected from *-Z2-arylene, *-Z2-heteroarylene, *-Z2-CI-2O alkylene, arylene, heteroarylene, C1-20 alkylene, C(O), S(O)2, *-OC(O) and *-N(R”)C(O), as defined above, or in which A3is as further defined in the preceding paragraphs, Q is polymer comprising n linker atoms which are oxygen atoms, wherein each of said oxygen atoms is attached to a group L. In this embodiment, Q may for instance be a polysaccharide. For instance Q may be chitin, a guar gum, gum arabic or a galactomannan, for instance locust bean gum (LBG). Such polysaccharides bear terminal OH groups which can be converted into said n linker atoms which are oxygen atoms.

[0471] More typically, however, the polymer of the invention of formula (II) is a compound of the following formula (XX)

[0472]

[0473] wherein R2and n are as defined herein, each R is a group comprising at least one of said groups for controlling SIRDRP, and Q is polystyrene or a copolymer comprising styrene repeat units (a styrene copolymer). Each sulfonylhydrazone group in the compound of formula (XX) is typically bonded to a phenyl group of said polystyrene or said copolymer comprising polystyrene.

[0474] The groups for controlling SIRDRP may be coupled to the polymer Q using similar coupling reactions as those described above for coupling the reactive intermediate precursor groups (or carbonyl precursors thereto) to the polymer Q.

[0475] Alternatively, the groups for controlling SIRDRP may be coupled to the reactive intermediate precursor groups, so that they are part of the group R rather than bonded directly to Q. As an example of the latter, a precursor to the compound of formula (XX) above in which R is NO2, R2is para-tolyl and Q is polystyrene, may be synthesised as described in Example 1 on page 142 of WO 2010 / 100410 Al, with reference to Fig. 6 of WO 2010 / 100410 Al. A group for controlling SIRDRP may then be introduced by reducing the NO2 group to amino group (NH2) and then by coupling the group for controlling SIRDRP to the amino group via routine coupling chemistry. For instance, in the final step of the synthesis an acid-halide-functionalised group for controlling SIRDRP may be reacted with the amino group to form an amide linkage to the group for controlling SIRDRP, such that each R, in the polymer of formula (XX) above, is a group comprising at least one of said groups for controlling SIRDRP. As another example of coupling the groups for controlling SIRDRP to the reactive intermediate precursor groups (so that they are part of the group R rather than bonded directly to Q), benzophenone groups may first be formed on a polystyrene backbone by treating polystyrene with benzoyl chloride and aluminium trichloride in a standard Friedel Crafts Acylation.

[0476] Subsequently, the terminal aryl groups of the benzophenones in the resulting polymer may be functionalised with a haloalkyl group, e.g. CH2CI or CFpBr, as described in Examples 1, 2, 3 and 9 hereinbelow. The halo of the halo-modified benzophenone groups may then be reacted with, e.g., a sulphur or oxygen nucleophile, to couple the halo-modified benzophenone groups with a group for controlling SIRDRP (see Example 9 hereinbelow). Alternatively, the halo of the halo-modified benzophenone groups may be converted into an amino group by a Delepine reaction (see Examples 1 and 2 hereinbelow) and then a group for controlling SIRDRP may be coupled to the amino group. For instance, an acid-halide-functionalised group for controlling SIRDRP may be reacted with the aminogroup to form an amide linkage to the group for controlling SIRDRP, as described in Examples 1 and 2 hereinbelow.

[0477] The ketone carbonyl group in the benzophenone moiety may be converted into a carbene precursor group either prior to or after coupling the group for controlling SIRDRP to the polymer, depending on the particular synthesis route employed. The carbonyl groups can be converted into hydrazone groups of formula (A), for instance, by treating the polymer comprising repeat units of formula (XB) with a compound of formula H2N-NHR1in the presence of heat, wherein R1is as defined above. The compound of formula H2N-NHR1may be hydrazine when R1is H, i.e. compound of formula H2N-NH2, or it may be a compound of formula H2N-N(H)S(O)2R2(when R1is -S(O)2R2) wherein R2is as defined above. Typically, the polymer comprising repeat units of formula (XB) is treated with H2N-NHR1in the presence of heat and a solvent. Any suitable solvent may be employed, for instance a polar protic solvent such as an alcohol. Typically, the solvent is methanol or ethanol. The reaction is carried out with heating, typically at the reflux temperature of the solvent used. For example, when the solvent is ethanol the reaction is suitably carried out at a temperature of 78 °C or higher, e.g. at a temperature of 80 °C. Typically, when R1is -S(O)2R2for instance tosyl, a few drops of concentrated sulfuric acid are also added to the reaction mixture before heating.

[0478] The carbonyl groups can be converted into diazo groups of formula (B) via hydrazone groups of formula (A). In other words, the carbonyl groups are first converted into hydrazone groups of formula (A), by the method described above (treating with a compound of formula H2N-NHR1in the presence of heat), and then the hydrazone groups of formula (A) are converted into diazo groups of formula (B).

[0479] The hydrazone groups of formula (A) can be converted into diazo groups of formula (B) by oxidation or elimination. Accordingly, in one embodiment the =N-NHR1hydrazone groups are converted into diazo groups, =N=N, by oxidation or elimination. In the cases where R1is -S(O)2R2, wherein R2is as defined above, an elimination reaction is performed. The elimination is typically achieved by treating the hydrazone compound with a basic compound such as an inorganic salt or a trialkylamine compound or, for instance the organic base l,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Usually, the inorganic salt is lithium hydroxide, sodium hydroxide or potassium hydroxide. Usually, the trialkylamine compound is triethylamine. DBU can be advantageous in certain applications as it is non-volatile. Typically, the treatment of the tosyl hydrazone compound with the base (for instance a trialkylamine compound) is carried out in the presence of a solvent. The solvent used is suitably a polar protic solvent such as an alcohol, for instance methanol or water. The treatment can be carried out with the tosyl hydrazone compound either in phase with the base, as a biphasic mixture, or as a suspension of tosyl hydrazone compound in a basic soloution.

[0480] In the case where R1is H, an oxidation reaction may be performed. Any suitable oxidant can be used to convert the hydrazone compound, in which Y is =N-NH2, into the corresponding diazomethane compound. Suitable oxidants include metal oxides, such as mercuric oxide, nickelperoxide, or hydrogen peroxide or chlorine (bleach). Typically, the oxidant is manganese oxide. More typically, this oxidation is conducted in the presence of a base, for instance a metal hydroxide and sodium sulphate. The metal hydroxide is typically an alkali metal hydroxide, for instance potassium hydroxide. A saturated solution of the metal hydroxide is generally used. The solvent used for the metal hydroxide is suitably a polar protic solvent such as an alcohol, for instance ethanol. The solvent used for the solution of the hydrazone compound is suitably a polar aprotic solvent, for instance tetrahydrofuran (THF) or an ether.

[0481] The carbonyl groups in the polymer can be converted into diazirine groups of formula (B) using known chemistry, for instance by using the procedure described in J. Am. Chem. Soc. 2020, 142, 52, 21743-21750. According to that procedure, the carbonyl groups, C=O in the polymer are first converted into N-tosyloxime groups, C=N-OTs. This is done by (i) treating the polymer with NFBOH’HCl in pyridine at 80 °C for 2 h, to convert the carbonyl groups C=O into oxime groups C=N(OH) and then (ii) treating the resulting oxime with -toluene sulfonylchloride (tosyl chloride) and ethylamine in acetone at 0 °C, and then stirring at room temperature for 3 hours, to convert the oxime groups C=N(OH) into N-tosyloxime groups, C=N-OTs. The N-tosyloxime groups, C=N-OTs, in the resulting polymer are then converted into diaziridine groups by treating a diethyl ether solution of the polymer with liquid ammonia at -78 °C for 2 hours. Finally, the diaziridine groups in the resulting polymer are then converted into diazirine groups of formula (B) by treating a dichloromethane solution of the diaziridine -containing polymer with triethylamine and iodine at 0 °C for 30 minutes. The resulting diazirine polymer is then extracted using dichloromethane, dried using MgSCft and purified.

[0482] As mentioned above, usually, when the reactive intermediate precursor groups are covalently bonded to the polymer backbone, each group for controlling SIRDRP is covalently bonded to a reactive intermediate precursor group. Thus, each group for controlling SIRDRP is covalently bonded to (a different) one of the reactive intermediate precursor groups. Thus, often, each of the reactive intermediate precursor groups is covalently bonded to the polymer backbone, and each of the groups for controlling SIRDRP is covalently bonded to a said reactive intermediate precursor group. Thus, preferably, in the polymer of the invention for treating a surface, each R, in the polymers of the invention of formula (II) is a group comprising at least one of said groups for controlling SIRDRP.

[0483] Usually, in this embodiment, the reactive intermediate precursor groups are often carbene precursor groups selected from hydrazone groups of formula (A), diazo groups of formula (B) and diazirine groups of formula (C):

[0484]

[0485] wherein R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-e alkyl group or an unsubstituted or substituted aryl group.

[0486] Preferably, the reactive intermediate precursor groups are hydrazone groups of formula (A)

[0487]

[0488] wherein R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-6 alkyl group or an unsubstituted or substituted aryl group, optionally wherein R1is a tosyl group.

[0489] Usually, R1is -S(O)2R2, wherein R2is as defined anywhere herein. In other words, usually the reactive intermediate precursor groups are sulfonylhydrazone groups. Typically, R2is phenyl substituted with Ci-6 alkyl. More typically, R2is phenyl substituted with methyl (i.e. tolyl). Often, R2is para-tolyl. Thus, R1in the hydrazone group of formula (A) is often a tosyl group.

[0490] The ability to generate a carbene from a sulfonylhydrazone group without isolating the diazo group intermediate provides numerous advantages. Such sulfonylhydrazone groups are particularly advantageous because they are capable of being converted into a carbene reactive intermediate group, yet they are more stable than the diazo groups of formula (B). In particular, they act as a protected precursor to the carbene reactive intermediate and thereby allow a greater level of control over unwanted degradation of the functionalized compound of the invention, such as in transport or storage. Of particular significance is the decreased toxicity of a sulfonylhydrazone group over a diazo group. Sulfonylhydrazone groups also offer a greater flexibility with regards to formulation as they are not degraded by carboxylic acids unlike diazo groups such as diazo esters, diazo ketones and alkyl or aryl diazos.

[0491] Thus, preferably, the polymer comprises n groups of formula (I)

[0492]

[0493] wherein

[0494] n is as defined herein;

[0495] each E, which is the same or different, is one of said carbene precursor groups (which may be as further defined anywhere herein);

[0496] each L, which is the same or different, is a single bond or a linker group (which may be as further defined anywhere herein); and

[0497] each R, which is the same or different, is a terminal group (which may be as further defined anywhere herein), or a group comprising at least one of said groups for controlling SIRDRP (which may be as further defined anywhere herein).The nature of terminal groups, and indeed the groups L, in the polymer of the invention for treating a surface is also not critical. Any suitable terminal group, R may be employed, and any suitable linker group, L, may be employed, or L may be a single bond. The terminal groups and the groups L may be as further defined anywhere herein. See in particular the definitions of the terminal groups R and the groups L above in relation to the polymer of the invention of formula (II), which are also applicable in relation to the groups of formula (I).

[0498] As mentioned above, preferably, in the polymer of the invention for treating a surface, each R is a group comprising at least one of said groups for controlling SIRDRP. Thus, preferably, in said n groups of formula (I), each R is a group comprising a said group for controlling SIRDRP. Each group for controlling SIRDRP may be as further defined anywhere herein.

[0499] Thus, often, the polymer of the invention for treating a surface comprises n groups of formula

[0500]

[0501] wherein

[0502] n is as defined anywhere herein;

[0503] each E, which is the same or different, is one of said carbene precursor groups (which may be as further defined anywhere herein);

[0504] each L, which is the same or different, is a single bond or a linker group (which may be as further defined anywhere herein); and

[0505] each R, which is the same or different, is a group comprising at least one of said groups for controlling SIRDRP (which may be as further defined anywhere herein).

[0506] Any suitable linker group, L, may be employed, or L may be a single bond. The L groups may be as further defined anywhere herein. See in particular the definitions of the groups L in relation to the polymer of the invention of formula (II), which are also applicable in relation to the groups of formula (I). Typically, in said n groups of formula (I), each L, which is the same or different, is a single bond or a linker group of formula (XII)

[0507]

[0508] wherein:

[0509] A1is bonded to E, wherein A1is bonded to the carbon atom bonded to R, wherein A1is: a single bond or an unsubstituted or substituted group selected from arylene, heteroarylene, Ci-20 perfluoroalkylene, *-0-Ci-2o alkylene, *-0-Ci-2o perfluoroalkylene, *-O-arylene, *-O-heteroarylene, *-N(R”)-CI-2O alkylene, *-N(R”)-CI-2O perfluoroalkylene, *-N(R”)-arylene, *-N(R”)-heteroarylene, *-S-Ci-2o alkylene, *-S-Ci-2o perfluoroalkylene, *-S-arylene, *-S-heteroarylene, *-C(R’)2-CI-2O alkylene, *-C(R’)2-CI-2O perfluoroalkylene, *-C(R’)2-arylene, *-C(R’)2-heteroarylene andCi-20 alkylene, wherein each R’ is independently selected from a halogen atom, Ci-io haloalkyl, Ci-io fluoroalkyl, Ci-w perfluoroalkyl, aryl, heteroaryl, C3-10 carbocyclyl, Cs-ioheterocyclyl, tri(Ci-io alkyl)silyl, aryldi(Ci-io alkyl)silyl, diaryl(Ci-io alkyl)silyl, triarylsilyl, C2-10 alkenyl, C2-10 alkynyl and Ci-10 alkyl, wherein * is the point of attachment of A1to E, wherein each of said C1-20 alkylene and C1-20 perfluoroalkylene groups is optionally interrupted by N(R”), O, S or arylene, and wherein R” is independently selected from H, Ci e alkyl and aryl;

[0510] A2is a single bond or an unsubstituted or substituted group selected from C1-20 alkylene, C1-20 perfluoroalkylene, arylene, heteroarylene, *-Ci-2o alkylene-(0-Ci-2o alkylene-)mwherein m is 1 to 20, *-Z1-Ci-2o alkylene, *-Z1-Ci-2o perfluoroalkylene, *-Z’-arylene, *-Z’ -heteroarylene and *-Z1-Ci-2o alkylene-(0-Ci-2o alkylene-)mwherein m is 1 to 20, wherein Z1is selected from O, S, C(O), S(O), S(O)2, N(R”), C(O)O, OC(O), C(O)N(R”) and N(R”)C(O), wherein * is the point of attachment of A2to A1, wherein each of said C1-20 alkylene and C1-20 perfluoroalkylene groups is optionally interrupted by N(R”), O, S or arylene, and wherein each R” is independently selected from H, Ci-e alkyl and aryl; and

[0511] A3is a single bond or an unsubstituted or substituted group selected from *-Z2-arylene, *-Z2-heteroarylene, *-Z2-CI-2O alkylene, arylene, heteroarylene, C1-20 alkylene, *-Z2-arylene-O, *-Z2-heteroarylene-O, *-Z2-CI-2O alkylene-O, *-arylene-O, *-heteroarylene-O, *-Ci-2o alkylene-O, C(O), S(O)2, *-OC(O), *-N(R”)C(O), O, S, N(R”), *-C(O)O, *-C(O)N(R”), *-S(O)2O, C120 alkenylene, Ci.

[0512] 20 alkynylene, *-Z2-CI-2O alkenylene and *-Z2-CI-2O alkynylene, wherein Z2is selected from O, S, N(R”), C(O), S(O), S(O)2, C(O)O, OC(O), C(O)N(R”) and N(R”)C(O), wherein each R” is independently selected from H, Ci-e alkyl and aryl, and wherein * is the point of attachment of A3to A2;

[0513] wherein at least one of A1, A2and A3is not a single bond, optionally wherein A1is not a single bond.

[0514] Each R in formula (I) is a group comprising at least one of said groups for controlling SIRDRP. Typically, each R is a group comprising one of said groups for controlling SIRDRP. Each group for controlling SIRDRP may be as further defined anywhere herein. In each R, it is typically the case that the group for controlling SIRDRP is attached to E (i.e. to the carbon atom in E that is also bonded to L) via an aryl group, for instance via a phenyl group. Also, optionally, there may be a spacer group between that aryl group and the group for controlling SIRDRP.

[0515] Thus, typically, in the polymer of the invention for treating a surface, each R is a group of formula -ArR-(SpR)p-RR, wherein Ar"- is an unsubstituted or substituted group selected from arylene and heteroarylene, wherein Ai^ is bonded to E; SpRis a spacer group; p is 0 or 1; and RRis a said group for controlling SIRDRP.

[0516] Often, Ai^ is unsubstituted arylene or unsubstituted heteroarylene. Typically, Ai^ is unsubstituted or substituted phenylene, for instance unsubstituted phenylene.When p is 1, the spacer group SpRis present. When p is 0, the spacer group SpRis absent and the group -Ar is bonded directly to RRas follows: -Ai^-R .

[0517] SpRis typically an unsubstituted or substituted group selected from C1-20 alkylene, C1-20 perfluoroalkylene, arylene, heteroarylene or -C1-20 alkylene-(0-Ci-2o alkylene-)mwherein m is 1 to 50, wherein each of said C1-20 alkylene and C1-20 perfluoroalkylene groups is optionally interrupted by N(R”), O, S or arylene, and wherein each R” is independently selected from H, C1-6 alkyl and aryl. SpRmay for instance be polypropylene glycol (PPG) or polyethylene glycol (PEG), for instance -CH2-CH2-(O-CH2-CH2-)mor -CH(CH3)-CH2-(O-CH2-CH(CH3)-)mor -CH2-CH(CH3)-(O-CH2-CH(CH3)-)m. Alternatively, SpRmay be a group of formula (XII) as defined in claim 14 provided that A1in the group of formula (XII) is bonded to Ai^, and A3in the group of formula (XII) is bonded to RR.

[0518] The group for controlling SIRDRP, RR, may be as further defined anywhere herein.

[0519] Often, in the polymer of the invention for treating a surface, for instance in each of said groups of formula (I), each R is a substituted aryl group or a substituted heteroaryl group, which substituted aryl or substituted heteroaryl group is, or comprises, one of said groups for controlling SIRDRP. The aryl or heteroaryl ring in said group may be part of the group for controlling SIRDRP -i.e. the aryl or heteroaryl ring may be necessary for the group for controlling SIRDRP to function as such. Thus, the aryl or heteroaryl ring, as well as its substituent(s), may together constitute the group for controlling SIRDRP. In that case, each substituted aryl group or substituted heteroaryl group, R, is one of said groups for controlling SIRDRP. Alternatively, the aryl or heteroaryl ring may simply be acting as a linker or spacer moiety, or it may be part of a larger a linker or spacer moiety, that links the carbene precursor group to the group for controlling SIRDRP. In that case, the group for controlling SIRDRP is only within the substituent group(s) on the aryl or heteroaryl ring. Thus, in that case, each substituted aryl group or substituted heteroaryl group, R, comprises one of said groups for controlling SIRDRP.

[0520] Hence, often, each R is a substituted aryl group or a substituted heteroaryl group, which substituted aryl or substituted heteroaryl group either (i) is, or (ii) comprises, one of said groups for controlling SIRDRP.

[0521] Typically, the substituted aryl group or substituted heteroaryl group is a substituted aryl group. Often, for instance, it is a substituted phenyl group.

[0522] Thus, typically, each R is a substituted phenyl group, which substituted phenyl group is, or comprises, one of said groups for controlling SIRDRP.

[0523] Typically, in the polymer of the invention for treating a surface, the n groups of formula (I) are n groups of formula (la)

[0524]

[0525] wherein:

[0526] n is as defined hereinbefore;

[0527] A is an aryl or heteroaryl ring which is bonded to E and X;

[0528] each E, which is the same or different, is one of said carbene precursor groups (which may be as further defined anywhere herein);

[0529] each L, which is the same or different, is a single bond or a linker group (which may be as further defined anywhere herein); and

[0530] each X is as defined below.

[0531] Alternatively, in the polymer of the invention for treating a surface, the n groups of formula (I) may be n groups of formula (lb)

[0532]

[0533] wherein:

[0534] n is as defined hereinbefore;

[0535] each E, which is the same or different, is one of said carbene precursor groups (which may be as further defined anywhere herein);

[0536] each L, which is the same or different, is a single bond or a linker group (which may be as further defined anywhere herein); and

[0537] each X is as defined below.

[0538] In formula (lb), each X may be bonded to any position (carbon atom) of the phenyl ring other than the position (carbon atom) that is bonded to E. Often, in formula (lb), each X is independently para relative to E or meta relative to E. For instance, in formula (lb), each X may be para to E. Alternatively, each X may be meta to E.

[0539] Often, in formula (la) and in formula (lb), each L is a single bond or a phenylene group. Typically, in formula (la) or (lb), each X is selected from any one of the following groups:

[0540]

[0541]

[0542] wherein

[0543] R1is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl, heteroaryl and ester;

[0544] R2is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;

[0545] X1is Br or Cl;

[0546] each of R3, R4and R5independently is hydrogen or an unsubstituted or substituted group selected from C O alkyl, aryl and heteroaryl;

[0547] X2is Br, Cl or I, and is preferably Br or Cl;

[0548] each of R42and R52independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;

[0549] each of R6and R7independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;

[0550] X3is Br, Cl or I, and is preferably Br or Cl;

[0551] each of R62and R72independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;

[0552] R8is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; and

[0553] X4is Br or Cl.

[0554] Thus, in formula (la) or (lb), each X may be a group of the following formula:

[0555]

[0556] wherein:

[0557] R1is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl, heteroaryl and ester; R2is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; and X1is Br, Cl or I.

[0558] Preferably X1is Br or Cl. More preferably, X1is Br.

[0559] Often, R1is hydrogen or an unsubstituted group selected from CMO alkyl, aryl, heteroaryl and ester, and R2is hydrogen or an unsubstituted group selected from CMO alkyl, aryl and heteroaryl.Typically, R1and R2are independently selected from hydrogen and unsubstituted C1-4 alkyl. For instance, R1and R2may be independently selected from hydrogen, methyl and ethyl, for instance from hydrogen and methyl. Often, R1and R2are both H, or R1is methyl and R2is H.

[0560] Alternatively, R1is often an ester, for instance -C(O)ORewherein Reis unsubstituted C1-4 alkyl, and R2is typically H. For instance, R1may be -C(O)OMe or -C(O)OEt and R2may be H.

[0561] Alternatively, each X in formula (la) or (lb) may be a group of any one of the following formulae:

[0562]

[0563] wherein:

[0564] each of R3, R4and R5independently is hydrogen or an unsubstituted or substituted group selected from C O alkyl, aryl and heteroaryl; and X2is Br, Cl or I.

[0565] Each of R42and R52independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl. Often, Each of R42and R52independently is hydrogen or an unsubstituted C1-4 alkyl. Usually, each of R42and R52is H.

[0566] Preferably X2is Br or Cl. More preferably, X2is Br.

[0567] Typically, each of R3, R4and R5independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl. R3is often H or unsubstituted or substituted C O alkyl. For instance, R3is often H or unsubstituted or substituted C1.4 alkyl. The substituted CMO alkyl (or C1.4 alkyl) may be aryl-substituted CMO alkyl (or aryl-substituted C1.4 alkyl), for instance phenylsubstituted CMO alkyl (or phenyl-substituted C1-4 alkyl), such as, for instance, benzyl. R3may for instance be H or unsubstituted or substituted C1-2 alkyl. R3may for instance be H or unsubstituted or substituted methyl. For instance, R3may be H, methyl or phenyl-substituted methyl (i.e. benzyl). Often, R3is H or benzyl. R3may be H. R3may be benzyl. Often, R4and R5are independently selected from hydrogen and unsubstituted C1.4 alkyl. For instance, R4and R5may be independently selected from hydrogen, methyl and ethyl, for instance from hydrogen and methyl. Often, both of R4and R5are unsubstituted C1-4 alkyl. For instance, R4and R5are preferably both methyl groups. Alternatively, R4may be H and R5may be methyl, or R4and R5are both H. Often, R3is H, R4is methyl and R5is methyl. Often, R3is benzyl, R4is methyl and R5is methyl.

[0568] Typically, each of R3, R4and R5independently is hydrogen or an unsubstituted group selected from CMO alkyl, aryl and heteroaryl. For instance, R3is often H or unsubstituted C1-4 alkyl, for example R3is often H or methyl. Often, R4and R5are independently selected from hydrogen and unsubstituted C1.4 alkyl. For instance, R4and R5may be independently selected from hydrogen,methyl and ethyl, for instance from hydrogen and methyl. Often, both of R4and R5are unsubstituted Ci-4 alkyl. For instance, R4and R5are preferably both methyl groups. Alternatively, R4may be H and R5may be methyl, or R4and R5are both H.

[0569] Alternatively, each X in formula (la) or (lb) may be a group of any one of the following formulae:

[0570]

[0571] wherein:

[0572] each of R6and R7independently is hydrogen or an unsubstituted or substituted group selected from Ci-io alkyl, aryl and heteroaryl; and

[0573] X3is Br, Cl or I.

[0574] Each of R62and R72independently is hydrogen or an unsubstituted or substituted group selected from C O alkyl, aryl and heteroaryl. Often, Each of R62and R72independently is hydrogen or an unsubstituted C1-4 alkyl. Usually, each of R62and R72is H.

[0575] Preferably X3is Br or Cl. More preferably, X3is Br.

[0576] Typically, each of R6and R7independently is hydrogen or an unsubstituted group selected from CMO alkyl, aryl and heteroaryl. Often, R6and R7are independently selected from hydrogen and unsubstituted C1.4 alkyl. For instance, R6and R7may be independently selected from hydrogen, methyl and ethyl, for instance from hydrogen and methyl. Often, both of R6and R7are unsubstituted C1-4 alkyl. For instance, R6and R7are preferably both methyl groups. Alternatively, R6may be H and R6may be methyl, or R6and R7are both H.

[0577] Alternatively, each X in formula (la) or (lb) may be a group the following formula:

[0578]

[0579] wherein

[0580] R8is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; and

[0581] X4is Br or Cl.

[0582] Typically, R8is hydrogen or an unsubstituted group selected from CMO alkyl, aryl and heteroaryl. For instance, R8is often hydrogen or unsubstituted C1.4 alkyl. R8may be H or methyl. Typically, R8is H.Alternatively, each X in formula (la) or (lb) may be a group of the following formula:

[0583]

[0584] wherein:

[0585] Z is -CH2O-, -CH2N(RV)-, O or N(RV) wherein Rvis hydrogen or an unsubstituted or substituted group selected from Ci-w alkyl, aryl and heteroaryl;

[0586] Ar1is an unsubstituted or substituted group selected from aryl and heteroaryl; and

[0587] R10is unsubstituted or substituted C1-20 alkyl.

[0588] Often, Z is N(RV). In other embodiments, however, Z may be O. Also, often, Z is -CH2O-. Rvis typically hydrogen or an unsubstituted group selected from C1-10 alkyl, aryl and heteroaryl. Rvis typically hydrogen or an unsubstituted C1-6 alkyl group, for instance H or unsubstituted C1.4 alkyl. Rvis often H, methyl or ethyl. Most typically, Rvis H.

[0589] Ar1may be an unsubstituted or substituted aryl group, for instance unsubstituted or substituted phenyl. Ar1is often an unsubstituted group selected from aryl and heteroaryl. Ar1is often an unsubstituted aryl group, for instance unsubstituted phenyl.

[0590] R10may be unsubstituted or substituted CMO alkyl, for instance unsubstituted or substituted C1-4 alkyl. Often, however, R10is unsubstituted C1-20 alkyl. R10may for instance be unsubstituted Cn 10 alkyl, for instance unsubstituted C1-6 alkyl or unsubstituted C1-4 alkyl. R10is often methyl or ethyl. Typically, R10is methyl.

[0591] Alternatively, each X in formula (la) or (lb) may be a group of the following formula:

[0592]

[0593] wherein:

[0594] each of R11, R12, R13and R14independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; and

[0595] Ar2is an unsubstituted or substituted group selected from aryl and heteroaryl.Ar2may be an unsubstituted or substituted aryl group, for instance unsubstituted or substituted phenyl. Ar2is often an unsubstituted group selected from aryl and heteroaryl. Ar2is often an unsubstituted aryl group, for instance unsubstituted phenyl.

[0596] Typically, R11and R12are independently selected from hydrogen and unsubstituted C1.4 alkyl. For instance, R11and R12may be independently selected from hydrogen, methyl and ethyl, for instance from hydrogen and methyl. Often, R11and R12are both H, or both methyl, or R11is methyl and R12is H.

[0597] Typically, R13and R14are independently selected from hydrogen and unsubstituted C1.4 alkyl. For instance, R13and R14may be independently selected from hydrogen, methyl and ethyl, for instance from hydrogen and methyl. Often, R13and R14are both H, or both methyl, or R13is methyl and R14is H.

[0598] Alternatively, each X in formula (la) or (lb) may be a group of the following formula:

[0599]

[0600] wherein:

[0601] LRis unsubstituted or substituted C1-20 alkylene, which C1-20 alkylene is optionally interrupted by O, OC(O) or N(R”)C(O) wherein R” is H, C1-6 alkyl or aryl; and

[0602] RRis unsubstituted or substituted C1-20 alkyl.

[0603] LRis often unsubstituted or substituted C1-10 alkylene, for instance unsubstituted or substituted C1-6 alkylene, or unsubstituted or substituted C1-4 alkylene. Typically, when LRis substituted, it is substituted with a cyano group (CN) and / or with at least one unsubstituted C1.4 alkyl group, for instance at least one methyl group. For instance, LRmay be substituted with both a cyano group and an unsubstituted C1-4 alkyl group, or with two unsubstituted C1.4 alkyl groups. LRmay for instance be substituted with both a cyano group and a methyl group. LRmay for instance be substituted with two methyl groups. LRmay for instance be a dimethyl methylene group, i.e. -C(CH3)2-. Often, however, LRis unsubstituted. LRis often unsubstituted C1-6 alkylene, for instance unsubstituted C1.4 alkylene, or unsubstituted C1-3 alkylene. For instance, LRmay methylene. LRis often uninterrupted. However, LRmay be interrupted by O, for instance, or by OC(O) or N(R”)C(O) wherein R” is H, C1-6 alkyl or aryl.

[0604] RRis often unsubstituted C1-20 alkyl. It may for instance be unsubstituted C5-15 alkyl. For example, RRmay be a -C12H25 group, i.e. a dodecyl group.

[0605] RRmay be an unsubstituted or substituted C1-6 alkyl group. RRmay for instance be an aryl- or heteroaryl- substituted C1-6 alkyl group such as, for instance, benzyl. RRmay for instance be substituted with an ester group, for instance -C(0)0CH3. RRmay for instance be substituted with bothan aryl group and an ester group; for instance, RRmay be -CH(Ph)C(0)0CH3. Alternatively, RRmay be an unsubstituted Ci-e alkyl group.

[0606] Alternatively, each X in formula (la) or (lb) may be a group of any one of the following formula:

[0607]

[0608] wherein:

[0609] Z is -CH2O-, -CH2N(RV)-, O or N(RV) wherein Rvis hydrogen or an unsubstituted or substituted group selected from Ci-w alkyl, aryl and heteroaryl;

[0610] RRis unsubstituted or substituted C1-20 alkyl; and

[0611] Lsis unsubstituted or substituted C1-20 alkylene.

[0612] Often, Z is N(RV). In other embodiments, however, Z may be O. Often, Z is -CH2O-.

[0613] Rvis typically hydrogen or an unsubstituted group selected from CMO alkyl, aryl and heteroaryl. Rvis typically hydrogen or an unsubstituted C1-6 alkyl group, for instance H or unsubstituted C1.4 alkyl. Rvis often H, methyl or ethyl. Most typically, Rvis H.

[0614] Lsis often unsubstituted or substituted CMO alkylene, for instance unsubstituted or substituted C1-6 alkylene, or unsubstituted or substituted C1-4 alkylene. Typically, when Lsis substituted, it is substituted with a cyano group (CN) and / or with at least one unsubstituted C1.4 alkyl group, for instance at least one methyl group. For instance, Lsmay be substituted with both a cyano group and an unsubstituted C1-4 alkyl group, or with two unsubstituted C1.4 alkyl groups. Lsmay for instance be substituted with both a cyano group and a methyl group. Lsmay for instance be a C2-4 alkylene group substituted with both a cyano group and a methyl group. Lsmay for instance be a -CH2-CH2-C(CH3)(CN)- group. Alternatively, Lsmay be substituted with two methyl groups. Lsmay for instance be a dimethyl methylene group, i.e. -C(CH3)2-.

[0615] RRis often unsubstituted C1-20 alkyl. It may for instance be unsubstituted C5-15 alkyl. For example, RRmay be a -C12H25 group, i.e. a dodecyl group.

[0616] RRmay be an unsubstituted or substituted C1-6 alkyl group. RRmay for instance be an aryl- or heteroaryl- substituted C1-6 alkyl group such as, for instance, benzyl. RRmay for instance be substituted with an ester group, for instance -C(0)0CH3. RRmay for instance be substituted with both an aryl group and an ester group; for instance, RRmay be -CH(Ph)C(O)OCH3. Alternatively, RRmay be an unsubstituted C1-6 alkyl group.

[0617] Alternatively, each X in formula (la) or (lb) may be a group of the following formula:

[0618]

[0619] wherein:

[0620] LRis unsubstituted or substituted C1-20 alkylene, which C1-20 alkylene is optionally interrupted by O, OC(O) or N(R”)C(O) wherein R” is H, Ci-e alkyl or aryl; and

[0621] each of Ruand RTindependently is an unsubstituted or substituted group selected from Ci-w alkyl, aryl and heteroaryl.

[0622] LRis often unsubstituted or substituted CMO alkylene, for instance unsubstituted or substituted C1-6 alkylene, or unsubstituted or substituted C1-4 alkylene. Typically, when LRis substituted, it is substituted with a cyano group (CN) and / or with at least one unsubstituted C1.4 alkyl group, for instance at least one methyl group. For instance, LRmay be substituted with both a cyano group and an unsubstituted C1-4 alkyl group, or with two unsubstituted C1.4 alkyl groups. LRmay for instance be substituted with both a cyano group and a methyl group. LRmay for instance be substituted with two methyl groups. LRmay for instance be a dimethyl methylene group, i.e. -C(CH3)2-. Often, however, LRis unsubstituted. LRis often unsubstituted C1-6 alkylene, for instance unsubstituted C1.4 alkylene, or unsubstituted C1-3 alkylene. For instance, LRmay methylene. LRis often uninterrupted. However, LRmay be interrupted by O, for instance, or by OC(O) or N(R”)C(O) wherein R” is H, C1-6 alkyl or aryl

[0623] Often, each of Ruand RTis independently an unsubstituted or substituted group selected from C1-6 alkyl and aryl. For instance, each of Ruand RTmay be independently selected from unsubstituted or substituted C1-6 alkyl and phenyl. Often, each of Ruand RTis independently selected from unsubstituted C1-6 alkyl and phenyl. For instance, often Ruis phenyl and RTis unsubstituted C1-6 alkyl. For instance, Rumay be phenyl and RTmay be methyl, ethyl or propyl. Alternatively, Ruand RTmay both be unsubstituted C1-6 alkyl, for instance they may both be methyl, ethyl or propyl, or for instance they may both be ethyl.

[0624] Alternatively, each X in formula (la) or (lb) may be a group of the following formula:

[0625]

[0626] wherein:

[0627] Z is -CH2O-, -CH2N(RV)-, O or N(RV) wherein Rvis hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;

[0628] Lsis unsubstituted or substituted C1-20 alkylene;each of Ruand RTindependently is an unsubstituted or substituted group selected from Ci-w alkyl, aryl and heteroaryl.

[0629] Often, Z is N(RV). In other embodiments, however, Z may be O. Often, Z is -CH2O-.

[0630] Rvis typically hydrogen or an unsubstituted group selected from C O alkyl, aryl and heteroaryl. Rvis typically hydrogen or an unsubstituted C1-6 alkyl group, for instance H or unsubstituted C1.4 alkyl. Rvis often H, methyl or ethyl. Most typically, Rvis H.

[0631] Lsis often unsubstituted or substituted CMO alkylene, for instance unsubstituted or substituted C1-6 alkylene, or unsubstituted or substituted C1-4 alkylene. Typically, when Lsis substituted, it is substituted with a cyano group (CN) and / or with at least one unsubstituted C1.4 alkyl group, for instance at least one methyl group. For instance, Lsmay be substituted with both a cyano group and an unsubstituted C1-4 alkyl group, or with two unsubstituted C1.4 alkyl groups. Lsmay for instance be substituted with both a cyano group and a methyl group. Lsmay for instance be a C2-4 alkylene group substituted with both a cyano group and a methyl group. Lsmay for instance be a -CH2-CH2-C(CH3)(CN)- group. Alternatively, Lsmay be substituted with two methyl groups. Lsmay for instance be a dimethyl methylene group, i.e. -C(CH3)2-.

[0632] Often, each of Ruand RTis independently an unsubstituted or substituted group selected from C1-6 alkyl and aryl. For instance, each of Ruand RTmay be independently selected from unsubstituted or substituted C1-6 alkyl and phenyl. Often, each of Ruand RTis independently selected from unsubstituted C1-6 alkyl and phenyl. For instance, often Ruis phenyl and RTis unsubstituted C1-6 alkyl. For instance, Rumay be phenyl and RTmay be methyl, ethyl or propyl. Alternatively, Ruand RTmay both be unsubstituted C1-6 alkyl, for instance they may both be methyl, ethyl or propyl, or for instance they may both be ethyl.

[0633] Alternatively, each X in formula (la) or (lb) may be a group of the following formula:

[0634]

[0635] wherein:

[0636] LRis unsubstituted or substituted C1-20 alkylene, which C1-20 alkylene is optionally interrupted by O, OC(O) or N(R”)C(O) wherein R” is H, C1-6 alkyl or aryl; and

[0637] Ar3is an unsubstituted or substituted group selected from aryl and heteroaryl.

[0638] LRis often unsubstituted or substituted CMO alkylene, for instance unsubstituted or substituted C1-6 alkylene, or unsubstituted or substituted C1-4 alkylene. Typically, when LRis substituted, it is substituted with a cyano group (CN) and / or with at least one unsubstituted C1.4 alkyl group, for instance at least one methyl group. For instance, LRmay be substituted with both a cyano group and an unsubstituted C1-4 alkyl group, or with two unsubstituted C1.4 alkyl groups. LRmay for instance be substituted with both a cyano group and a methyl group. LRmay for instance be substituted with twomethyl groups. LRmay for instance be a dimethyl methylene group, i.e. -C(CHs)2-. Often, however, LRis unsubstituted. LRis often unsubstituted Ci-6 alkylene, for instance unsubstituted C1.4 alkylene, or unsubstituted C1-3 alkylene. For instance, LRmay methylene. LRis often uninterrupted. However, LRmay be interrupted by O, for instance, or by OC(O) or N(R”)C(O) wherein R” is H, C1-6 alkyl or aryl.

[0639] Ar3may be an unsubstituted or substituted aryl group, for instance unsubstituted or substituted phenyl. Ar3is often an unsubstituted group selected from aryl and heteroaryl. Ar3is often an unsubstituted aryl group, for instance unsubstituted phenyl.

[0640] Alternatively, each X in formula (la) or (lb) may be a group of the following formula:

[0641]

[0642] wherein:

[0643] Z is -CH2O-, -CH2N(RV)-, O or N(RV) wherein Rvis hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;

[0644] Lsis unsubstituted or substituted C1-20 alkylene; and

[0645] Ar3is an unsubstituted or substituted group selected from aryl and heteroaryl.

[0646] Often, Z is N(RV). In other embodiments, however, Z may be O. Often, Z is -CH2O-.

[0647] Rvis typically hydrogen or an unsubstituted group selected from CMO alkyl, aryl and heteroaryl. Rvis typically hydrogen or an unsubstituted C1-6 alkyl group, for instance H or unsubstituted C1.4 alkyl. Rvis often H, methyl or ethyl. Most typically, Rvis H.

[0648] Lsis often unsubstituted or substituted CMO alkylene, for instance unsubstituted or substituted C1-6 alkylene, or unsubstituted or substituted C1-4 alkylene. Typically, when Lsis substituted, it is substituted with a cyano group (CN) and / or with at least one unsubstituted C1.4 alkyl group, for instance at least one methyl group. For instance, Lsmay be substituted with both a cyano group and an unsubstituted C1-4 alkyl group, or with two unsubstituted C1.4 alkyl groups. Lsmay for instance be substituted with both a cyano group and a methyl group. Lsmay for instance be a C2-4 alkylene group substituted with both a cyano group and a methyl group. Lsmay for instance be a -CH2-CH2-C(CH3)(CN)- group. Alternatively, Lsmay be substituted with two methyl groups. Lsmay for instance be a dimethyl methylene group, i.e. -C(CH3)2-.

[0649] Ar3may be an unsubstituted or substituted aryl group, for instance unsubstituted or substituted phenyl. Ar3is often an unsubstituted group selected from aryl and heteroaryl. Ar3is often an unsubstituted aryl group, for instance unsubstituted phenyl.

[0650] Alternatively, each X in formula (la) or (lb) may be a group of the following formula:

[0651]

[0652] wherein:

[0653] LRis unsubstituted or substituted C1-20 alkylene, which C1-20 alkylene is optionally interrupted by O, OC(O) or N(R”)C(O) wherein R” is H, Ci-e alkyl or aryl; and

[0654] each of Ruand RTindependently is an unsubstituted or substituted group selected from Ci-w alkyl, aryl and heteroaryl.

[0655] LRis often unsubstituted or substituted CMO alkylene, for instance unsubstituted or substituted C1-6 alkylene, or unsubstituted or substituted C1-4 alkylene. Typically, when LRis substituted, it is substituted with a cyano group (CN) and / or with at least one unsubstituted C1.4 alkyl group, for instance at least one methyl group. For instance, LRmay be substituted with both a cyano group and an unsubstituted C1-4 alkyl group, or with two unsubstituted C1.4 alkyl groups. LRmay for instance be substituted with both a cyano group and a methyl group. LRmay for instance be substituted with two methyl groups. LRmay for instance be a dimethyl methylene group, i.e. -C(CH3)2-. Often, however, LRis unsubstituted. LRis often unsubstituted C1-6 alkylene, for instance unsubstituted C1.4 alkylene, or unsubstituted C1-3 alkylene. For instance, LRmay methylene. LRis often uninterrupted. However, LRmay be interrupted by O, for instance, or by OC(O) or N(R”)C(O) wherein R” is H, C1-6 alkyl or aryl.

[0656] Often, each of Ruand RTis independently an unsubstituted or substituted group selected from C1-6 alkyl and aryl. For instance, each of Ruand RTmay be independently selected from unsubstituted or substituted C1-6 alkyl and phenyl. Often, each of Ruand RTis independently selected from unsubstituted C1-6 alkyl and phenyl. For instance, often Ruis phenyl and RTis unsubstituted C1-6 alkyl. For instance, Rumay be phenyl and RTmay be methyl, ethyl or propyl. Alternatively, Ruand RTmay both be unsubstituted C1-6 alkyl, for instance they may both be methyl, ethyl or propyl, or for instance they may both be ethyl.

[0657] Alternatively, each X in formula (la) or (lb) may be a group of the following formula:

[0658]

[0659] wherein:

[0660] Z is -CH2O-, -CH2N(RV)-, O or N(RV) wherein Rvis hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;

[0661] Lsis unsubstituted or substituted C1-20 alkylene; andeach of Ruand RTindependently is an unsubstituted or substituted group selected from Ci-w alkyl, aryl and heteroaryl.

[0662] Often, Z is N(RV). In other embodiments, however, Z may be O. Often, Z is -CH2O-.

[0663] Rvis typically hydrogen or an unsubstituted group selected from C O alkyl, aryl and heteroaryl. Rvis typically hydrogen or an unsubstituted C1-6 alkyl group, for instance H or unsubstituted C1.4 alkyl. Rvis often H, methyl or ethyl. Most typically, Rvis H.

[0664] Lsis often unsubstituted or substituted CMO alkylene, for instance unsubstituted or substituted C1-6 alkylene, or unsubstituted or substituted C1-4 alkylene. Typically, when Lsis substituted, it is substituted with a cyano group (CN) and / or with at least one unsubstituted C1.4 alkyl group, for instance at least one methyl group. For instance, Lsmay be substituted with both a cyano group and an unsubstituted C1-4 alkyl group, or with two unsubstituted C1.4 alkyl groups. Lsmay for instance be substituted with both a cyano group and a methyl group. Lsmay for instance be a C2-4 alkylene group substituted with both a cyano group and a methyl group. Lsmay for instance be a -CH2-CH2-C(CH3)(CN)- group. Alternatively, Lsmay be substituted with two methyl groups. Lsmay for instance be a dimethyl methylene group, i.e. -C(CH3)2-.

[0665] Often, each of Ruand RTis independently an unsubstituted or substituted group selected from C1-6 alkyl and aryl. For instance, each of Ruand RTmay be independently selected from unsubstituted or substituted C1-6 alkyl and phenyl. Often, each of Ruand RTis independently selected from unsubstituted C1-6 alkyl and phenyl. For instance, often Ruis phenyl and RTis unsubstituted C1-6 alkyl. For instance, Rumay be phenyl and RTmay be methyl, ethyl or propyl. Alternatively, Ruand RTmay both be unsubstituted C1-6 alkyl, for instance they may both be methyl, ethyl or propyl, or for instance they may both be ethyl.

[0666] Alternatively, each X in formula (la) or (lb) may be a group of the following formula:

[0667]

[0668] wherein:

[0669] each of R15and R16independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; and

[0670] each of R17and R18independently is an unsubstituted or substituted group selected from C O alkyl, aryl and heteroaryl.

[0671] Often, each of R15and R16is independently selected from H and an unsubstituted or substituted group selected from C1-6 alkyl and aryl. Typically, R15and R16are independently selected from H and unsubstituted or substituted C1-6 alkyl. More typically, R15and R16are independentlyselected from H and unsubstituted Ci-e alkyl. Often, R15and R16are independently selected from H and methyl. Typically, R15and R16are both H.

[0672] Often, each of R17and R18is independently an unsubstituted or substituted group selected from Ci-6 alkyl and aryl. For instance, each of R17and R18may be independently selected from unsubstituted or substituted Ci-6 alkyl and phenyl. Often, R17and R18are independently selected from unsubstituted Ci-6 alkyl and phenyl. Usually, R17and R18are both unsubstituted Ci-6 alkyl, for instance they may both be methyl, ethyl or propyl. Often, R17is ethyl and R18is ethyl.

[0673] For instance, in formula (la) or (lb), each X may be selected from any one of the following

[0674]

[0675]

[0676] For instance, in formula (la) or (lb), each X may be selected from any one of the above groups and any one of the following groups:

[0677]

[0678]

[0679] groups:

[0680]

[0681] Alternatively, for instance, each X in formula (la) or (lb) may be the following group:

[0682]

[0683] Usually, when the polymer of the invention for treating a surface comprises n groups of formula (I), (la) or (lb), L, in each of said groups of formula (I), (la) or (lb), is bonded to a polymer backbone. The polymer backbone may be as defined anywhere herein. Thus, the polymer backbone to which each L is bonded may be a hydrocarbon backbone, for instance a hydrocarbon chain, such as an alkylene chain, or for instance poly(styrene). Alternatively, it may for instance be polyethylenimine (PEI), such as branched PEI or hyperbranched PEI. The backbone may comprise more than one type of repeat unit. It may for instance be a copolymer backbone. Thus, the polymer backbone may be a homo-polymer or a copolymer. Often the polymer backbone is one that comprises aryl or heteroaryl rings, since the carbene precursor groups, E, in formulae (I), (la) and (lb) may easily be attached to such rings via L, whether L is a single bond or a linker group. Typically, said aryl or heteroaryl rings are aryl rings. Usually, said aryl rings are phenyl rings. Examples of polymers that comprise aryl rings that are suitable for the polymer backbone include, for instance, polystyrene, a copolymer comprising polystyrene, a thermoplastic elastomer, polyisoprene, a copolymer comprising polyisoprene, SBS rubber, SIS rubber or poly(styrene)-poly(ethylene / butylene)-poly(styrene) (SEBS). Other examples of polymers that may be employed as the backbone of the polymer of the invention for treating a surface, include condensation polymers and addition polymers. For instance, polysaccharides, including but not limited to chitin, guar gums, gum arabic, galactomannans, or for instance locust bean gum (LBG), may be employed as the backbone. Proteins, including but not limited to Keratin, may be employed as the backbone. Polyesters, including but not limited to Nylon, polyethylene terephthalate (PET), polyoxyethylene terephthalate (POET) or a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate (PET-POET), may be employed as the backbone. Polyethers, including but not limited to polypropylene glycol (PPG), polyethylene glycol (PEG), Polyethylene oxide (PEO), may be employed as the backbone. Polyolefins, including but not limited to polyethylene (PE), polypropylene (PP), and co-polymers thereof may be employed as the backbone. Polyolefin co-polymers, may be employed as the backbone. Polyacrylates and polymethacrylates, including but not limited to polyacric acid (PAA) polymethacrylic acid (PMAA), Poly2 -dimethylamino methacrylate (PDMAEMA), Poly-2 -hydroxyethyl methacylate (PHEMA), acrylonitrile, may be employed as the backbone. Polystyrene may be employed as the backbone. Thermoplatic elastomers, including but not limited to, Polybutadiene, Polyisoprene, SBS rubber and SIS rubber, may be employed as the backbone. Polycarbonates may be employed as the backbone. Polyetheretherketone (PEEK) may be employed as the backbone. Polyetherimides may be employed as the backbone. Polyimides may be employed as the backbone. Polysulfones may be employed as thebackbone. Poly vinyl chloride (PVC) may be employed as the backbone. Polysilanes, Polysiloxanes, and Polyureas may be employed as the backbone. Polyurethanes may be employed as the backbone. Polylactic acid may be employed as the backbone. Polyvinylidene chloride may be employed as the backbone. Fluoro-polymers, including but not limited to PTFE (polytetrafluoroethylene), PFA (perfluoroalkoxy polymer resin), fluorinated ethylene -propylene and PVDF (Kynar) may be employed as the backbone. Polyethylene imines, for instance branched polyethyleneimine, or hyper branched polyethyleneimine may be employed as the backbone.

[0684] Often, when the polymer of the invention for treating a surface comprises n groups of formula (I), (la) or (lb), L, in each of said groups of formula (I), (la) or (lb), is bonded to a polymer backbone wherein the polymer backbone is a linear or branched polymer or copolymer. Typically, the polymer backbone comprises polystyrene or polyethylenimine (PEI), optionally wherein the PEI is branched PEI or hyper-branched PEI.

[0685] A wide range of molecular weights, Mn, are possible for the polymer of the invention considering that the number of repeat units of the polymer backbone, may, for instance, be as low as, say, from three to ten, or, say, as high as 500,000. The molecular weight (Mn) of the polymer of the invention for treating a surface may for instance be at least 1,000 Da, or for instance at least 1,500 Da. In some cases the molecular weight is higher. Often, for instance, the Mnof the polymer is at least 2,000 Da, for instance at least 5,000 Da, or at least 10,000 Da. The Mnof the polymer of the invention may be as high as 250 MDa, for instance less than or equal to 100 MDa, less than or equal to 20 MDa, less than or equal to 10 MDa, or less than or equal to 1 MDa. More typically, the Mnof the polymer of the invention is less than or equal to 500 kDa, for instance less than or equal to 100 kDa, or less than or equal to 50 kDa.

[0686] Often, the molecular weight (Mn) of the polymer of the invention is from 1,000 Da to 500,000 Da, for instance from 1,000 Da to 300,000 Da, or for instance, from 1,000 Da to 100,000 Da. The Mnof the polymer comprising repeat units of formula (X) may for instance be from 1,000 Da to 50,000 Da, or for instance from 1,500 Da to 30,000 Da, from 2,000 Da to 20,000 Da, or from 2,500 Da to 10,000 Da.

[0687] In other embodiments, the Mnof the polymer comprising repeat units of formula (X) may for instance be from 1,000 Da to 20,000 Da, or for instance from 1,500 Da to 10,000 Da, from 1,000 Da to 5,000 Da, or from 1,000 Da to 3,000 Da. Such relatively low molecular weight polymers of the invention can be desirable when the polymer of the invention is being used for treating a porous substrate, particularly for instance a membrane or filter with small pores. Using such a relatively low molecular weight polymer helps to ensure that the surface treatment will not block the pores of the substrate.

[0688] Often, the number of repeat units in the polymer backbone of such a low molecular weight polymer will be, say, from 5 to 50, or for instance from 10 to 40, from 10 to 30, or from 5 to 20, for instance from 10 to 20.Often, the polymer of the invention for treating a surface comprises repeat units of formula (lip)

[0689]

[0690] wherein each Y is a group of formula (I) as defined anywhere herein.

[0691] Typically, the number of said repeat units of formula (Up) in the polymer of the invention is n, wherein n may be as defined anywhere herein.

[0692] The polymer of the invention for treating a surface may optionally further comprise repeat units other than the repeat units of formula (lip) . For instance, the polymer of the invention for treating a surface may optionally further comprise, in addition to the repeat units of formula (lip), repeat units of formula (IIIp) :

[0693]

[0694] Often, each Y, in the repeat units of formula (lip), is a group of formula (la) as defined anywhere herein. For instance, each Y, in the repeat units of formula (lip), may be a group of formula (lb) as defined herein.

[0695] Often, for instance, each Y is a group of formula (lb)

[0696]

[0697] wherein each E, which is the same or different, is a carbene precursor group (which may be as further defined anywhere herein, and may for instance be a tosyl hydrazone group), and preferably each L is a single bond, and each X is selected from the X groups defined herein.

[0698] Often, each X is a group of formula

[0699]

[0700] wherein each of R3, R4and R5independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; X2is Br or Cl; and each of R42and R52independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl. Often, X2is Br. Typically, each of R3, R4and R5independently is hydrogen or an unsubstituted or substituted group selected from C O alkyl, aryl and heteroaryl. R3is often H or unsubstituted or substituted CMO alkyl. For instance, R3is often H or unsubstituted or substituted C1-4 alkyl. The substituted CMO alkyl (or C1-4 alkyl) may be aryl-substituted CMO alkyl (or aryl-substituted C1-4 alkyl), for instance phenyl-substituted CMO alkyl (or phenyl-substituted C1-4 alkyl), such as, for instance, benzyl. R3may for instance be H or unsubstituted or substituted C1-2 alkyl. R3may for instance be H or unsubstituted or substituted methyl. For instance, R3may be H, methyl or phenyl-substituted methyl (i.e. benzyl). Often, R3is H or benzyl. R3may be H. R3may be benzyl. Often, R4and R5are independently selected from hydrogen and unsubstituted C1-4 alkyl. For instance, R4and R5may be independently selected from hydrogen, methyl and ethyl, for instance from hydrogen and methyl. Often, both of R4and R5are unsubstituted C1.4 alkyl. For instance, R4and R5are preferably both methyl groups. Alternatively, R4may be H and R5may be methyl, or R4and R5are both H. Often, R3is H, R4is methyl and R5is methyl. Often, R3is benzyl, R4is methyl and R5is methyl. Usually, each of R42and R52is H. Typically, each of R3, R4and R5independently is hydrogen or an unsubstituted group selected from CMO alkyl, aryl and heteroaryl. For instance, R3is often H or unsubstituted C1.4 alkyl, for example R3is often H or methyl. Often, R4and R5are independently selected from hydrogen and unsubstituted C1.4 alkyl. For instance, R4and R5may be independently selected from hydrogen, methyl and ethyl, for instance from hydrogen and methyl. Often, both of R4and R5are unsubstituted C1-4 alkyl. For instance, R4and R5are preferably both methyl groups.

[0701] Alternatively, R4may be H and R5may be methyl, or R4and R5are both H. Usually, each of R42and R52is H.

[0702] Each X may for instance comprise the group:

[0703]

[0704] Each X may for instance be:

[0705]

[0706] Each X may for instance be:

[0707]

[0708] Alternatively, each X is often selected from any one of the following groups:

[0709]

[0710]

[0711] wherein

[0712] Z is -CH2O-, -CH2N(RV)-, 0 or N(RV) wherein Rvis hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;

[0713] Ar1is an unsubstituted or substituted group selected from aryl and heteroaryl;

[0714] R10is unsubstituted or substituted C1-20 alkyl;

[0715] each of R11, R12, R13and R14independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;

[0716] Ar2is an unsubstituted or substituted group selected from aryl and heteroaryl;

[0717] LRis unsubstituted or substituted C1-20 alkylene, which C1-20 alkylene is optionally interrupted by O, OC(O) or N(R”)C(O) wherein R” is H, Ci-e alkyl or aryl;

[0718] RRis unsubstituted or substituted C1-20 alkyl;

[0719] Lsis unsubstituted or substituted C1-20 alkylene;

[0720] each of Ruand RTindependently is an unsubstituted or substituted group selected from Ci-w alkyl, aryl and heteroaryl;

[0721] Ar3is an unsubstituted or substituted group selected from aryl and heteroaryl; and each of R17and R18independently is an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl.

[0722] Each of these groups may be as further defined herein.

[0723] Polymers of formula (Up) may be synthesised as detailed in Examples 1, 2, 3 and 5 herein, by Friedel Crafts Acylation to introduce benzophenone groups into polystyrene and then functionalising the aryl groups of resulting polymer with a haloalkyl groups. The halo of the haloalkyl may then be further functionalised to introduce an SIRDRP group as described in Example 1, 2, 4 or 9. As a final step, the ketone is converted into a carbene precursor group, e.g. into a tosylhydrazone group as described in the Examples or into a diazo or a diazirine group as described above. Another route to such compounds is to prepare tosylhydrazone-fimctionalised polystyrene as described in Fig. 6 and Example 1 (on page 142) of WO 2010 / 100410 Al, and then couple groups for controlling SIDRP to the aryl groups of that polymer through derivatization of the nitro groups. The skilled person isreadily able to modify these methods to introduce a wide variety of groups for controlling SIDRP, with a wide variety of linkers and spacers.

[0724] Process for producing a treated substrate

[0725] The invention also provides a process for producing a treated substrate, which treated substrate has a surface suitable for surface-initiated reversible-deactivation radical polymerization (SIRDRP), which process comprises:

[0726] (a) contacting a surface of a substrate with a polymer for treating a surface, wherein the polymer for treating a surface comprises:

[0727] n reactive intermediate precursor groups, wherein n is an integer equal to or greater than 3; and m groups for controlling SIRDRP, wherein m is an integer equal to or greater than 3, wherein: the groups for controlling SIRDRP are selected from groups which comprise an initiator and groups which comprise a chain transfer agent (CTA); and

[0728] the reactive intermediate precursor groups are selected from carbene precursor groups and nitrene precursor groups, wherein the carbene precursor groups are selected from hydrazone groups of formula (A), diazo groups of formula (B) and diazirine groups of formula (C), and the nitrene precursor groups are azide groups of formula (D):

[0729] wherein

[0730]

[0731] an unsubstituted or substituted aryl group; and

[0732] (b) generating carbene or nitrene reactive intermediate groups from the reactive intermediate precursor groups, so that the carbene or nitrene reactive intermediate groups react with the surface of the substrate.

[0733] In the process of the invention for producing a treated substrate, the polymer for treating a surface may be as further defined anywhere herein for the polymer of the invention.

[0734] A wide variety of substrates may be treated in accordance with the process of the invention, to introduce an initiator or CTA functionality onto a surface of the substrate, and thereby render the surface suitable for SIRDRP.

[0735] The substrate may be in any suitable physical form, for instance in the form of a solid film, layer, sheet or board. Alternatively, the substrate may be in powder form, or in the form of pellets, beads, particles, nanoparticles or microparticles. The pellets, beads or particles may be macroscopic particles, i.e. visible to the naked eye, or microscopic particles. Thus, the particles could be microparticles or nanoparticles.The substrate may therefore be a particle, pellet or bead, or a plurality of particles, pellets or beads. Often, the substrate is a particle, or a plurality of particles. Similarly, it may be a bead, or a plurality of beads. Similarly, the substrate may be a pellet, or a plurality of pellets. The or each particle, bead or pellet may be non -porous or porous. The substrate may for instance be a porous particle, or a plurality of porous particles.

[0736] Alternatively, the substrate is often a solid film, layer, or sheet. The substrate may for instance be a flexible film, layer, or sheet.

[0737] The substrate may be non-porous or porous.

[0738] Often, the substrate is porous.

[0739] The substrate is often a solid film, layer, or sheet, which is porous. The porous substrate may for instance be a flexible porous film, a flexible porous layer, or a flexible porous sheet.

[0740] The substrate may for instance be a membrane, for instance a flexible membrane. The membrane may be a porous membrane, for instance a flexible, porous membrane. Alternatively, it may be a non-porous membrane. Often, however, the substrate is a porous membrane.

[0741] The porous substrate may for instance be a filter.

[0742] Thus, typically, the substrate is a porous membrane or a filter.

[0743] The substrate is typically insoluble in water and thermally stable. The substrate is usually, for instance, stable at temperatures of up to 100 °C at least, and is preferably stable at temperatures significantly higher than that. It may for instance be able to withstand temperatures of up to 200 °C, or up to 400 °C, or 600 °C, or even up to 1000 °C or 2000 °C, without degrading or melting. It is usually a porous substrate, e.g. a porous membrane or filter.

[0744] The substrate is typically stable (i.e. it will not dissolve or degrade) in pH-neutral water (or aqueous solution) at temperatures up to and including 100 °C. It is preferably also stable (i.e. will not dissolve or degrade) in alkaline water (or aqueous solution) at temperatures up 100 °C, and / or in acidic water (or aqueous solution) at temperatures up 100 °C. It is usually a porous substrate, e.g. a porous membrane or filter. It may be a flexible porous membrane or a flexible filter.

[0745] When the substrate is a porous membrane, it may for instance have a thickness of from 1 pm to 500 pm. Often, for instance the porous membrane has a thickness of from 5 pm to 500 pm, for instance a thickness of from 10 pm to 500 pm.

[0746] The porous substrate may for instance have a porosity of from 0.1 % to 50 %. More often, however, the porosity of the substrate is from 0.2 % to 30 %, for instance from 0.5 % to 20 %, or more typically from 0.5 % to 15 %. The pore size of the porous substrate, as used herein, refers to the mean pore size of the pores in the porous substrate. The porous substrate may for instance have a pore size of from 0.2 pm to 100 pm. More often, however, the pore size of the substrate is from 0.5 pm to 100 pm, for instance from 0.5 pm to 40 pm, or more typically from 0.5 pm to 20 pm. The pore size of the porous substrate may for instance be from 1 pm to 20 pm.The substrate may for instance be a porous membrane, for instance a mesh, such as a polymer mesh, for instance a nylon mesh, having a porosity and pore size as defined in the preceding paragraphs.

[0747] In general, the substrate may be made of a wide variety of materials. The substrate may, for instance comprise a polymer, glass or ceramic. The substrate may for instance comprise any of the following materials:

[0748] - natural or synthetic polymers including but not limited to cellulose, polyglycosides, polypeptides, polyacrylates, polyacrylics, polyamides, polyimides, polycarbonates, polyesters, epoxy resins, polyethers, polyketones, polyolefins, rubbers, polystyrenics, polysulfones, polyurethanes, polyvinyls and their co-polymers;

[0749] - polyesters, polyacrylates, polyolefins, polyamides, polyimides, polysulfones and epoxy resins, homopolymers and copolymers of ethylene, propylene, styrene, PET (polyethylene terephthalate) or EPDM (ethylene propylene diene monomer);

[0750] - homopolymers and copolymers, for instance a block copolymers;

[0751] - thermoplastic resins and thermosetting resins;

[0752] - inorganic materials including but not limited to metals, metal alloys, metal salts, silica, glasses, alumina, titania, and allotropes of carbon such as diamond, diamond-like carbon, graphite, fullerenes and nanotubes;

[0753] - Ceo and nanotubes, for instance carbon nanotubes;

[0754] - textiles and paper.

[0755] The substrate may comprise woven or non-woven fibres. The woven or non-woven fibres may comprise a polymer, glass or ceramic. The woven or non-woven fibres may form a mesh.

[0756] Often, the substrate comprises a polymer. The substrate may for instance comprise woven or non-woven fibres, which fibres comprise a polymer. The polymer fibres may together form a mesh. Thus, the substrate may be a polymer mesh.

[0757] When the substrate comprises a polymer, the polymer may, for instance, comprise, or be, polyphenylene sulphide (PPS), Nylon, polyethylene, polyetheretherketone (PEEK), polysulfone, polyvinylidene fluoride (PVDF) or polypropylene. It may comprise, or be, a natural polymer, for instance cellulose.

[0758] The substrate may for instance be a porous polymer membrane. The porous polymer membrane may be a polymer mesh. The porosity and pore size of the porous polymer membrane (which may be a polymer mesh) may be as defined above. The porous polymer membrane may comprise Nylon, polyphenylene sulphide (PPS), polyethylene, polyetheretherketone (PEEK), polysulfone, polyvinylidene fluoride (PVDF), cellulose or polypropylene. The porous polymer membrane may for instance comprise woven or non-woven fibres, which fibres comprise Nylon,polyphenylene sulphide (PPS), polyethylene, polyetheretherketone (PEEK), polysulfone, polyvinylidene fluoride (PVDF), cellulose or polypropylene. The membrane may for instance be a mesh of polymer fibres which comprise Nylon, polyphenylene sulphide (PPS), polyethylene, polyetheretherketone (PEEK), polysulfone, polyvinylidene fluoride (PVDF), cellulose or polypropylene.

[0759] Often, in the process of the invention, contacting a surface of the substrate with the polymer for treating a surface comprises contacting the surface of the substrate with a composition comprising the polymer for treating a surface. The composition is typically a liquid. Thus, often, the composition comprising the polymer for treating a surface, comprises both said polymer and a solvent. A wide range of solvents are suitable, and any suitable solvent may be employed. The solvent is often for instance a polar solvent, for instance a polar organic solvent. The solvent may be a polar protic solvent. The solvent is often an alcohol. The solvent may for instance be methanol or ethanol. The solvent may alternatively be a polar aprotic solvent, for instance acetone. When the composition further comprises a solvent, the total solids content of the precursor composition is typically from 0.01 % by weight to 50 % by weight, for instance from 0.01 % by weight to 25 % by weight, from 0.02 % by weight to 10% by weight, or from 0.02 % by weight to 5% by weight. When the composition further comprises a solvent, the total solids content of the precursor composition is typically from 0.1 % by weight to 50 % by weight, for instance from 0.2 % by weight to 25 % by weight, or from 0.5 % by weight to 10% by weight. Often, the composition comprising the polymer further comprises an alkylammonium compound, for instance a tetraalkylammonium compound. The compound is typically a hydroxide. Thus the composition comprising the polymer may for instance further comprise a tetraalkylammonium hydroxide, such as, for example tetraethylammonium hydroxide.

[0760] Typically, in the process of the invention, contacting the surface of the substrate with the polymer for treating a surface comprises disposing said composition comprising the polymer on the surface of the substrate. Disposing said composition on the surface of the substrate often comprises coating the surface of the substrate with said composition. The disposing, or coating, of the composition on the surface of the substrate may comprise dipping the substrate in the composition, drop-coating the substrate with the composition, spray-coating the substrate with the composition, or spin-coating the substrate with the composition. The disposing, or coating, of the composition on the surface of the substrate may comprise coating the composition on said surface using a metering bar. A metering bar is preferred for non-porous substrates. Often, for a porous substrate, the disposing, or coating, of the composition on the surface of the substrate comprises dipping the substrate in the composition. When the composition comprising the polymer further comprises a solvent, the process may further comprise a solvent removal step. Often, the solvent is removed by heating the composition on the substrate. This may be referred to as a drying step. Said heating is typically at a temperature of less than 100 °C, for instance from 40 °C to 80 °C, or from 50 °C to 70 °C, and is carried out for about 5 to 20 minutes, for instance about 10 minutes. Often, however, a solventremoval step is not carried out and, once the composition comprising the polymer and a solvent has been disposed on the surface of the substrate, the next part of the process is carried out, i.e. (b) generating carbene or nitrene reactive intermediate groups from the reactive intermediate precursor groups, so that the carbene or nitrene reactive intermediate groups react with the surface of the substrate.

[0761] When the substrate is a porous substrate, for instance a porous membrane or a fdter, contacting the surface of the substrate with the polymer typically comprises contacting any “external” surface of the substrate, and any “internal” surface of the porous support material, with the polymer, including the inside walls of the pores of the porous substrate. Thus, usually, the step of disposing or coating said composition comprising the polymer on the surface of the substrate comprises disposing or coating said composition on an external surface of the substrate and an internal surface of the substrate, for instance on the inside walls of pores in the substrate. Thus, the composition comprising the polymer may coat an internal surface of the porous substrate and an external surface of the porous substrate. In particular, the composition may coat walls of pores within the porous substrate. It may also coat an external surface of the porous substrate. Usually, however, the composition does not fdl the pores of a porous substrate, but only provides a thin coating on the pore walls. In this way, the substrate can retain its porosity, i.e. the pores are not blocked by the polymer being disposed on the surface of the substrate.

[0762] The process of the invention further comprises (b) generating carbene or nitrene reactive intermediate groups from the reactive intermediate precursor groups, so that the carbene or nitrene reactive intermediate groups react with the surface of the substrate.

[0763] The conditions for decomposition of azide groups to form reactive nitrene intermediate groups, and for hydrazone, diazo or diazirine groups to form reactive carbene intermediate groups are discussed hereinbefore. The carbene or nitrene reactive intermediate groups are typically generated from the reactive intermediate precursor groups by athermal process and / or by an irradiation process, but can be generated chemically. Typically, the carbene or nitrene reactive intermediate groups are generated by thermal irradiation, for instance by heating. This heat might be applied to the polymer for treating a surface externally, for example by using a hot press, but may also be as a result of another process, for example, extrusion. Alternatively, the reactive intermediate groups may be generated by electromagnetic radiation, for instance by UV, microwave or laser irradiation, or by ultrasonic irradiation.

[0764] Thus, typically, in the process of the invention, generating carbene or nitrene reactive intermediate groups from the reactive intermediate precursor groups comprises heating the polymer or irradiating the polymer.

[0765] Often, in the process of the invention, the carbene or nitrene reactive intermediate groups are generated by thermal irradiation, for instance by heating. Thus, in the process of the invention,generating carbene or nitrene reactive intermediate groups from the reactive intermediate precursor groups typically comprises heating the polymer for treating a surface.

[0766] Heating the polymer for treating a surface may comprise heating the polymer under elevated pressure, or while applying pressure. For instance, it may comprise heating the polymer using a hot press.

[0767] Heating the polymer for treating a surface often comprises heating the polymer at a temperature of at least 80 °C, for instance at a temperature of at least 100 °C, for instance at a temperature of from 80 °C to 200 °C, or at a temperature of from 100 °C to 150 °C, for instance at a temperature of from 100 °C to 115 °C. Sometimes, heating the polymer at this temperature comprises heating the polymer at the temperature while applying pressure to the polymer, for instance using a hot press.

[0768] The process typically further comprises washing the treated substrate. The treated substrate may for instance be washed in a polar solvent, for instance water, typically deionised water. A mixture of water and one or more polar organic solvents (for instance acetone and / or an alcohol such as methanol) may be employed. This washing step may help to remove any excess uncured coating. Following said washing, the process may further comprise drying the treated substrate, for instance drying it at a temperature of from 40 °C to 100°C, for instance from 50 °C to 90 °C. The treated substrate may be dried at said temperature for a duration of, for instance, 15-120 minutes.

[0769] The result of generating carbene or nitrene reactive intermediate groups from the reactive intermediate precursor groups, is that the carbene or nitrene reactive intermediate groups react with the surface of the substrate, to bond the polymer to the substrate. Generally, the carbene or nitrene reactive intermediate groups also crosslink the polymer, which advantageously reduces its solubility in polar solvents including water, preferably to render it insoluble and resistant to solvent swelling. In this way, a robust coating is bonded to the substrate surface very strongly, and the substrate surface is thereby functionalised with initiator or CTA groups to render the surface suitable for carrying out surface -initiated reversible-deactivation radical polymerization (SIRDRP) thereon.

[0770] Thus, typically, in the process of the invention, the carbene or nitrene reactive intermediate groups react with the surface of the substrate to bond the polymer to the surface of the substrate. More typically, the carbene or nitrene reactive intermediate groups react with the surface of the substrate and with the polymer to crosslink the polymer and to bond the polymer to the surface of the substrate.

[0771] The invention further provides a treated substrate which is obtainable by a process of the invention as defined above. Such a treated substrate has a surface suitable for carrying out surface-initiated reversible-deactivation radical polymerization (SIRDRP) thereon.

[0772] The process of the invention for producing the treated substrate may further comprise performing surface -initiated reversible-deactivation radical polymerization (SIRDRP) on the treated substrate.Thus, in some embodiments, the process of the invention further comprises: (c) exposing the surface suitable for surface -initiated reversible -deactivation radical polymerization to one or more monomers, and polymerising the one or monomers on the surface by surface-initiated reversible-deactivation radical polymerization (SIRDRP). The one or more monomers are of course exposed to the surface suitable for SIRDRP under conditions suitable for carrying out SIRDRP, and such conditions are known in the art. Examples 6 and 7 herein provide examples of such conditions for ATRP.

[0773] The SIRDRP may be performed under a covering layer which is disposed on the surface suitable for surface -initiated reversible-deactivation radical polymerization. The covering layer is typically disposed on the surface suitable for SIRDRP after the surface has been exposed to the one or more monomers under conditions suitable for carrying out SIRDRP. The covering layer typically comprises an inert material. The covering layer is typically impermeable to air. The covering layer is often an inorganic material, for instance glass. The covering layer may for instance be a glass layer, such as for instance a glass slide (for example as employed in Example 7 herein). The inventors have found that such a covering layer advantageously avoids the need to purge the RDRP solution with nitrogen. Thus, often the process further comprises (c) exposing the surface suitable for surface-initiated reversible-deactivation radical polymerization to one or more monomers, disposing a covering layer on the surface, and polymerising the one or monomers on the surface and under the covering layer by surface-initiated reversible -deactivation radical polymerization. The covering layer may for instance be a glass layer.

[0774] The one or more monomers may, for instance, comprise a monomer which comprises an ionic group, for instance a cationic group or an anionic group. The ionic group may for instance be a sulfonic acid group (as defined herein, i.e. a group including the sulfonate anion, including sulfonic acid in its protonated or deprotonated form, and any salt thereof). The monomer which comprises an ionic group may for instance be a methacrylate, or acrylate, monomer comprising the ionic group. The one or more monomers may, for instance, comprise sulfopropyl methacrylate, for instance, sulfopropyl methacrylate potassium salt. Sulfopropyl methacrylate can advantageously be used to provide sulfonic acid groups, as defined herein, on the surface of the substrate (which may for instance be a porous substrate).

[0775] In this way, molecules of a polymer of interest can be grown by SIRDRP on a treated substrate produced in accordance with the process of the present invention.

[0776] The type of reversible-deactivation radical polymerization employed for the SIRDRP may be as further defined herein. For instance, the reversible-deactivation radical polymerization employed for the SIRDRP may be atom transfer radical polymerisation (ATRP), reversible additionfragmentation chain transfer (RAFT) polymerisation, photoiniferter-mediated polymerisation (PIMP), nitroxide -mediated radical polymerisation (NMP), iniferter polymerisation, catalytic chain transfer polymerisation, cobalt mediated radical polymerisation (CMRP), iodine -transfer polymerization (ITP)or copper-based reversible -deactivation radical polymerization (Cu-based RDRP). The conditions for SIRDRP using these types of RDPR are well known, and may be employed in conjunction with the treated substrates of the present invention. Examples of conditions that may be employed for ATRP, for instance, are provided in Examples 6 and 7 herein.

[0777] The invention further provides a treated substrate which has a polymer grown thereon by SIRDRP, which is obtainable by the process of the invention having steps (a), (b) and (c) as defined herein. The polymer grown thereon by SIRDRP may comprise ionic groups, for instance cationic groups or anionic groups. It may for instance comprise sulfonic acid groups. It may for instance be a methacrylate polymer or copolymer, or an acrylate polymer or copolymer, which comprises such ionic groups. The polymer may for instance be poly(sulfopropyl methacrylate) or a copolymer thereof.

[0778] The invention also provides a treated substrate having a surface suitable for surface-initiated reversible-deactivation radical polymerization (SIRDRP), wherein the treated substrate comprises:

[0779] (a) a substrate; and

[0780] (b) a reacted polymer disposed on a surface of the substrate,

[0781] wherein the reacted polymer is obtainable by generating carbene or nitrene reactive intermediate groups from reactive intermediate precursor groups of a polymer for treating a surface, so that the carbene or nitrene reactive intermediate groups react with said surface of the substrate, wherein the polymer for treating a surface comprises n of said reactive intermediate precursor groups, wherein n is an integer equal to or greater than 3, and m groups for controlling SIRDRP, wherein m is an integer equal to or greater than 3, wherein:

[0782] the groups for controlling SIRDRP are selected from groups which comprise an initiator and groups which comprise a chain transfer agent (CTA); and

[0783] the reactive intermediate precursor groups are selected from carbene precursor groups and nitrene precursor groups, wherein the carbene precursor groups are selected from hydrazone groups of formula (A), diazo groups of formula (B) and diazirine groups of formula (C), and the nitrene precursor groups are azide groups of formula (D):

[0784]

[0785] wherein R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-6 alkyl group or an unsubstituted or substituted aryl group.

[0786] In the treated substrate of the invention, the polymer for treating a surface may be as further defined anywhere herein. Similarly, in the treated substrate of the invention, the substrate may be asfurther defined anywhere herein. The substrate may for instance be a porous material or a particle. The porous material is often a filter or a membrane.

[0787] Since the polymer for treating a surface bears at least 3 reactive intermediate precursor groups which can be converted into carbene or nitrene reactive intermediate groups, one molecule of the polymer for treating a surface can react with two, or three, or more molecules of another compound or material - for instance with the substrate and with further molecules of the polymer itself - to form crosslinks that bond the materials together. Thus, the crosslinker compound can react both with itself and with any other material or materials with which it is brought into contact, including of course the substrate surface, to form a strong, three-dimensional cross-linked network that is covalently-bonded. In this way, a robust coating comprising initiator or CTA functionalities is provided on the surface of the substrate.

[0788] For instance, the polymer for treating a surface employed in the present invention may be brought into contact with the substrate, and the reactive intermediate precursor groups of the polymer for treating a surface may then be converted into reactive carbene or nitrene intermediate groups, thereby causing the polymer for treating a surface to react with itself intermolecularly, and to react with the surface of the substrate, thereby forming a cross-linked network between polymer molecules, which network is also bonded to the surface of substrate. Note that when the substrate is porous, bonding to the surface of substrate can, and typically does, include bonding to the internal surface of the porous substrate as well as to the porous substrate’s external surface. Thus the bonding to the surface of a porous substrate typically includes bonding to the walls of pores within the porous substrate. In the resulting network, the reacted polymer bonds polymer molecules to each other and to the surface of the substrate. If further compounds or materials are also in contact with the polymer for treating a surface when the reactive carbene or nitrene intermediate groups are generated, then they too will be incorporated into the crosslinked network that becomes bonded to the substrate.

[0789] The reacted polymer disposed on the surface of the substrate may bond to any part of the surface of the substrate. When the substrate is porous it may bond to any part of the external surface of the porous substrate or to any part of the internal surface of the porous substrate, i.e. to inside walls of pores within the porous substrate. In this way, the reacted polymer may penetrate through the pores of a porous substrate, e.g. from one side of a porous substrate to another. The reacted polymer may only be bonded to part of the surface of a substrate, for instance a porous substrate, or it may for example be bonded to the whole of the surface of the substrate, for instance to the whole of the surface of a porous substrate. Thus the reacted polymer may cover, and be bonded to, the entire surface of the porous support material including the surfaces inside the pores of the porous support material, thereby providing all such surfaces with initiator and / or CTA functionalities suitable for RDRP, and rendering the surfaces suitable for carrying out SIRDRP.

[0790] The invention further provides a treated substrate which comprises:

[0791] (a) a substrate;(b) a reacted polymer disposed on a surface of the substrate; and

[0792] (c) a further polymer, grown by surface -initiated reversible-deactivation radical polymerization (SIRDRP), bonded to the reacted polymer (b),

[0793] wherein the reacted polymer is obtainable by generating carbene or nitrene reactive intermediate groups from reactive intermediate precursor groups of a polymer for treating a surface, so that the carbene or nitrene reactive intermediate groups react with said surface of the substrate, wherein the polymer for treating a surface comprises n of said reactive intermediate precursor groups, wherein n is an integer equal to or greater than 3, and m groups for controlling SIRDRP, wherein m is an integer equal to or greater than 3, wherein:

[0794] the groups for controlling SIRDRP are selected from groups which comprise an initiator and groups which comprise a chain transfer agent (CTA); and

[0795] the reactive intermediate precursor groups are selected from carbene precursor groups and nitrene precursor groups, wherein the carbene precursor groups are selected from hydrazone groups of formula (A), diazo groups of formula (B) and diazirine groups of formula (C), and the nitrene precursor groups are azide groups of formula (D):

[0796]

[0797] wherein R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-e alkyl group or an unsubstituted or substituted aryl group,

[0798] and wherein the further polymer, grown by SIRDRP, is obtainable by exposing the reacted polymer (b) to one or more monomers, and polymerising the one or monomers by surface -initiated reversible-deactivation radical polymerization.

[0799] In the treated substrate of the invention, the polymer for treating a surface may be as further defined anywhere herein, as may be the resulting reacted polymer disposed on the surface of the substrate. Similarly, in the treated substrate of the invention, the substrate may be as further defined anywhere herein. The substrate may for instance be a porous material or a particle. The porous material is often a filter or a membrane.

[0800] The step(s) of exposing the reacted polymer (b) to one or more monomers, and polymerising the one or monomers on the surface by surface-initiated reversible-deactivation radical polymerization (SIRDRP) is of course carried out under conditions suitable for carrying out SIRDRP, and such conditions are known in the art. Examples 6 and 7 herein provide examples of such conditions for ATRP. The inventors have found that the SIRDRP may advantageously be performed under a covering layer, e.g. a glass slide, as discussed above.The one or more monomers may, for instance, comprise a monomer which comprises an ionic group, for instance a cationic group or an anionic group. The ionic group may for instance be a sulfonic acid group. The monomer which comprises an ionic group may for instance be a methacrylate, or acrylate, monomer comprising the ionic group. The one or more monomers may, for instance, comprise sulfopropyl methacrylate, for instance sulfopropyl methacrylate potassium salt.

[0801] In this way, molecules of a polymer of interest can be grown by SIRDRP on a treated substrate produced in accordance with the process of the present invention. The type of reversible -deactivation radical polymerization employed for the SIRDRP may be as further defined herein. For instance, the reversible-deactivation radical polymerization employed for the SIRDRP may be atom transfer radical polymerisation (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerisation, photoiniferter-mediated polymerisation (PIMP), nitroxide -mediated radical polymerisation (NMP), iniferter polymerisation, catalytic chain transfer polymerisation, cobalt mediated radical polymerisation (CMRP), iodine -transfer polymerization (ITP) or copper-based reversible-deactivation radical polymerization (Cu-based RDRP). The conditions for SIRDRP using these types of RDPR are well known, and may be employed in conjunction with the treated substrates of the present invention, to produce a treated substrate which additionally comprises a further polymer, grown by surface-initiated reversible-deactivation radical polymerization (SIRDRP), bonded to the reacted polymer (b). Examples of conditions that may be employed for ATRP, for instance, are provided in Examples 6 and 7 herein.

[0802] The further polymer, grown by SIRDRP, may comprise ionic groups, for instance cationic groups or anionic groups. It may for instance comprise sulfonic acid groups. It may for instance be a methacrylate polymer or copolymer, or an acrylate polymer or copolymer, which comprises such ionic groups. The polymer may for instance be poly(sulfopropyl methacrylate) or a copolymer thereof.The invention is further described in the following examples.EXAMPLES

[0803] Example 1: Preparation of a Surface Treatment Polymer comprising an ATRP Initiator

[0804]

[0805] Scheme 1. Preparation of a surface treatment polymer comprising an ATRP Initiator

[0806] With reference to Scheme 1 above, a standard Friedel Crafts Acylation is performed on polystyrene, by treating polystyrene, in a suitable solvent, with 4-methyl benzoyl chloride and aluminium trichloride. Benzophenone groups are thereby formed on the polymer backbone. The aryl methyl group of the resulting product is then subjected to a thermal free radical bromination, using N-Bromosuccinimide (NBS), to install a bromo group on the methyl. A Delepine reaction is thenperformed on the resulting product, using hexamethylenetetramine followed by acidic hydrolysis (e.g. using HC1) to convert the bromo group into a primary amine. Amidation of the primary amine is then carried out, using bromo isobutyryl bromide, to install an ATRP initiator. The resulting product is then treated with toluene sulfonyl hydrazide (tosyl hydrazide) in order to convert the benzophenone ketone into the corresponding tosyl hydrazone moiety, a precursor to a carbene reactive intermediate .

[0807] Example 2: Preparation of a further Surface Treatment Polymer comprising an ATRP Initiator

[0808]

[0809] Scheme 2. Preparation of a further surface treatment polymer comprising an ATRP InitiatorWith reference to Scheme 2 above, a standard Friedel Crafts Acylation is performed on polystyrene, by treating polystyrene, in a suitable solvent, with benzoyl chloride and aluminium trichloride.

[0810] Benzophenone groups are thereby formed on the polymer backbone. Then, a chloromethylation of the pendant aromatic rings in the resulting product is carried out by treatment of the resulting product with formaldehyde and zinc chloride. A Delepine reaction is then performed on the resulting product, using hexamethylenetetramine followed by acidic hydrolysis (e.g. using HC1) to convert the chloro group into a primary amine. Amidation of the primary amine is then carried out, using bromo isobutyryl bromide, to install an ATRP initiator. The resulting product is then treated with toluene sulfonyl hydrazide (tosyl hydrazide) in order to convert the benzophenone ketone into the corresponding tosyl hydrazone moiety, a precursor to a carbene reactive intermediate.

[0811] Example 3: Preparation of a Surface Treatment Polymer (1) comprising an ATRP Initiator

[0812]

[0813] Scheme 3. Preparation of a surface treatment polymer (1) comprising an ATRP Initiator

[0814] With reference to Scheme 3 above, a standard Friedel-Crafts acylation is performed by dissolving polystyrene (25.31g, 243.0mmol) an p-toluoyl chloride (26.38g, 170.0mmol) in toluene (120ml). Once a solution is formed aluminium trichloride (23.8g, 178mmol) is added to the mixture portion wise with stirring over 30mins, a dark green solution is formed. The mixture is heated with stirring to 40°C for 3 days before being cooled and quenched with 1.2M HCI (128g). The organic phase wascollected, concentrated in vacuo and the product isolated by precipitation into isopropanol, followed by fdtration and drying to furnish the benzophenone modified polystyrene (39.5g, 87% yield, modification level x=70%).

[0815] This material was radically brominated by first drying a solution of benzoyl peroxide (1 lOmg, 73wt% in water) and chloroform (9.6ml) with anhydrous magnesium sulphate. The benzophenone modified polystyrene (1.5g, 5.64mmol), benzoyl peroxide solution (8ml, 0.05eq) and N-bromo succinimide (2.56g, 14.4mmol) were mixed together under a nitrogen atmosphere. The resulting solution was heated to 75°C with stirring while being irradiated with a 5W LED light source 15cm away from the flask. After 66 hours the solution was cooled to room temperature and quenched with water and dichloromethane. The organic layer was collected, washed with water, and concentrated in vacuo to yield the bromated product (1.607g). Analysis shows bromination does not go to completion with evidence of brominated aromatic methyl groups present.

[0816] Finally, the benzophenone is converted though to the corresponding tosyl hydrazone using standard acidic condensation conditions to prevent unwanted side reactions. Thus to a slurry of the brominated polymer (1.51g), p-toluene sulfonyl hydrazide (1.15g) in chlorobenzene (4.4g) was added concentrated hydrochloric acid (37%, lOOpL) and the suspension heated to 75°C. The resulting solution was heated with stirring for a 2.5h, cooled to room temperature then concentrated in vacuo to yield an oil. The product was isolated by precipitation using isopropanol followed by filtration, washing with water and drying of the resulting solid to yield desired product (1) (1.85g).

[0817] Example 4: Preparation of a Surface Treatment Polymer (2) comprising an amide linked ATRP Initiator

[0818]

[0819] Scheme 4. Preparation of a surface treatment polymer (2) comprising an amide linked ATRP InitiatorWith reference to Scheme 4 above a mixture of benzyl amine (1.59ml, 11.4mmol), a-bromoisobutyryl bromide (2.50g, 10.9mmol), triethylamine (1.59ml, 11.4mmol) in dichloromethane are stirred together at room temperature for 3h. the mixture was quenched with 1.2M HC1 (25ml) and the organic layer collected and concentred in vacuo to yield the benzyl amide tertiary bromide product.

[0820] The bromomethyl benzophenone polystyrene formed in Example 3 (1.5g 1.84mmol), benzyl amide tertiary bromide (0.944g, 3.67mmol), tetrabutylammonium iodide (1.36g, 3.674mmol) and potassium phosphate tribasic (780mg, 3.57mmol) were suspended in acetonitrile (5ml). The mixture was heated to 50°C with stirring for 18h. The resulting suspension was diluted with acetonitrile (3ml), concentrated hydrochloric acid (37%, 860pL) and p-toluene sulfonyl hydrazide (0.901g, 7.33mmol) was added. The resulting mixture was stirred at 75°C for 3h before being cooled and diluted with dichloromethane (10ml). The organic layer was collected, washed with 1.2M HC1 and concentrated in vacuo to yield an oil. Isopropanol was added to the oil and the resulting solid collected by filtration and dried to yield product (2) (2.49g).

[0821] Example 5: Surface Treatment of a Substrate using a Polymer of the Invention

[0822] A solution of the carbene precursor material (e.g. as produced by the method of Example 1 , Example 2, Example 3 or Example 4) was suspended in methanol at a solids content between 0.02% and 5% (for example, 1%) and activated using tetraethylammonium hydroxide (35% w / w). The solution was stirred until a solution formed and then coated onto the desired substrate using a metering bar. A metering bar is preferred for non-porous substrates. Alternatively, a dip bath is preferred instead of a metering bar for porous substrates (such as membranes). The coated substrate was cured at between 100°C and 115 °C (for instance at 115 °C) for 30mins then washed with acetone, methanol and water.

[0823] Example 6: General ATRP Polymerisation process

[0824] An ATRP solution was prepared by dissolving CuBr2, 2,2-bipryridine (Bpy) and suflopropyl methacrylate potassium salt (SPMA) in 4: 1 methanol: water. These were at a molar ratio of 500: 10: 1 monomer: Bpy : CuBr2.

[0825] The coated and washed substrate from Example 3 was submerged in the ATRP solution, and the container was sealed. The solution was purged of air by bubbling with N2 for a minimum of 30 minutes. In a separate container, ascorbic acid (AA) was weighed out and dissolved in 4: 1 MeOELEEO. Ascorbic acid was added at a molar ratio of 20: 1 AA:CuBr2 (200: 1 monomer:AA). This solution of AA was also purged with N2 before being added to the ATRP solution under N2 bysyringe. The ATRP reaction mixture containing the coated substrate was mixed thoroughly and the reaction was allowed to proceed for a determined amount of time.

[0826] After given time, the reaction was stopped by opening the container to air and removing the substrate from the reaction mixture. The substrate was washed thoroughly by methanol and water several times and dried in a desiccator. For further washing to ensure all non-grafted polymer is removed, the substrate was soaked overnight in water. The substrate was removed and washed before drying by desiccator.

[0827] The process of Example 6 can be used for introducing a sulfonic acid onto porous substrates.

[0828] Example 7: General ATRP Polymerisation process to introduce a sulfonic acid on porous or non-porous substrate

[0829] A stock monomer / catalyst solution was prepared containing 0.739g sulfopropyl methacrylate potassium salt, Copper chloride (0.0013g) andl,l,4,7,7-pentamethyldiethylenetriamine (PMDETA) (4pL) in water ( 1 ,5ml) . The substrate was washed thoroughly with acetone, methanol and water to remove any unbound material or byproduct and placed on a glass petri dish.

[0830] Ascorbic acid (0.0013g) was dissolved in water (0.5ml) and to this solution was added the stock solution (0.741g). The mixture was shaken quickly before being applied to the surface of the substrate. A glass slide was immediately applied over the surface of the coated substrate and the reaction allowed to stand at room temperature for 18h. The glass slide was removed, and the substrate was washed thoroughly with water and methanol several times to remove unreacted monomer or catalysts.

[0831] Example 8: Determination of ATRP modification using water contact angle

[0832] The success of the ATRP was measured by examining the change in water angle after ATRP has taken place. Samples which had not been treated with surface modifications of the invention (using compound 1 from Example 3 or compound 2 from Example 4) showed similar water contact angles before and after ATRP, whereas those which had been treated with surface modifications of the invention showed reductions in water contact angle after ATRP. If the substrate is porous in nature this allows a higher degree of functionalisation and thus lower contact angles post ATRP.

[0833]

[0834] Example 9: Preparation of Surface Treatment Polymers comprising RAFT or PIMP agents

[0835]

[0836] Scheme 5. Preparation of halo-modified-benzophenone-containing polystyrenes 1 and 2With reference to scheme 5, compound 1 is prepared by first performing a standard Friedel Crafts Acylation on polystyrene, by treating polystyrene, in a suitable solvent, with benzoyl chloride and aluminium trichloride. Benzophenone groups are thereby formed on the polymer backbone. Then, a chloromethylation of the pendant aromatic rings in the resulting product is carried out by treatment of the resulting product with formaldehyde and zinc chloride, to form compound 1.

[0837] Compound 2 is prepared by first performing a standard Friedel Crafts Acylation on polystyrene, by treating polystyrene, in a suitable solvent, with 4 -methyl benzoyl chloride and aluminium trichloride. Benzophenone groups are thereby formed on the polymer backbone. The aryl methyl group of the resulting product is then subjected to athermal free radical bromination, using N-Bromosuccinimide (NBS), to install a bromo group on the methyl and thereby produce compound 2.

[0838]

[0839] Scheme 6. Preparation of surface treatment polymers comprising RAFT or PIMP agents from the halo-modified-benzophenone-containing polystyrenes 1 and 2.With reference to scheme 6. first, a RAFT or PIMP active compound is coupled by reaction of a sulphur or oxygen nucleophile with one of the halo-modified benzophenones 1 or 2. Such RAFT- and PIMP -active compounds, and their coupling reactions with halo alkyl groups, are known in the art.

[0840] See, for instance, B. de Boer et al., Macromolecules 2000, 33, 349-356, which describes the use of sodium N,N-diethyldithiocarbamate (STC) in a coupling reaction to form a iniferter. The nucleophilic N,N-diethyldithiocarbamate moiety of STC can be reacted with the halo-modified benzophenone 1 or 2 to replace the halo group with the N,N-diethyldithiocarbamate and thereby install a PIMP -active iniferter. See also Takolpuckdee, P. et al., Org. Lett., Vol. 7, No. 16, 2005, pp. 3449-3452, which describes the coupling of RAFT-active agents S-Methoxycarbonyl-phenylmethyl 2-Hydroxyethyl trithiocarbonate (MCPHT), 3 -(Methoxy carbonyl phenylmethyl sulfanylthio carbonyl sulfanyl) propionic acid (MPPA), and 3 -(Benzylsulfanyl thiocarbonylsulfanyl) propionic acid (BSPA) to Merrifield resins by reaction with the pendant CH2CI groups on the resins. MCPHT, MPPA and BSPA can similarly be reacted with the halo-modified benzophenone 1 or 2 to install a RAFT-active group in place of the halo.

[0841] In each case, the resulting product is then treated with toluene sulfonyl hydrazide (tosyl hydrazide) in order to convert the benzophenone ketone into the corresponding tosyl hydrazone moiety, a precursor to a carbene reactive intermediate.

Claims

CLAIMS1. A polymer for treating a surface, which polymer comprises:n reactive intermediate precursor groups, wherein n is an integer equal to or greater than 3; andm groups for controlling surface -initiated reversible -deactivation radical polymerization (SIRDRP), wherein m is an integer equal to or greater than 3, wherein:the groups for controlling SIRDRP are selected from groups which comprise an initiator and groups which comprise a chain transfer agent (CTA); andthe reactive intermediate precursor groups are selected from carbene precursor groups and nitrene precursor groups, wherein the carbene precursor groups are selected from hydrazone groups of formula (A), diazo groups of formula (B) and diazirine groups of formula (C), and the nitrene precursor groups are azide groups of formula (D):wherein R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-e alkyl group or an unsubstituted or substituted aryl group.

2. A polymer according to claim 1 wherein n is an integer equal to or greater than 5.

3. A polymer according to claim 1 or claim 2 wherein the ratio of the number of reactive intermediate precursor groups, n, in the polymer to the number of groups for controlling SIRDRP, m, in the polymer, n:m, is at least 0.5: 1, and is preferably at least 1:1.

4. A polymer according to any one of claims 1 to 3 wherein the groups for controlling SIRDRP are:(a) groups which comprise an initiator for atom transfer radical polymerisation (ATRP);(b) groups which comprise a CTA for reversible addition-fragmentation chain transfer (RAFT) polymerisation and / or groups which comprise an initiator for RAFT polymerisation;(c) groups which comprise an initiator for photoiniferter-mediated polymerisation (PIMP) and / or groups which comprise a CTA for PIMP;(d) groups which comprise an initiator for nitroxide-mediated radical polymerisation (NMP); (e) groups which comprise an initiator for iniferter polymerisation, wherein the initiator is an iniferter;(f) groups which comprise a CTA for catalytic chain transfer polymerisation and / or groups which comprise an initiator for catalytic chain transfer polymerisation;(g) groups which comprise a CTA for cobalt mediated radical polymerisation (CMRP) and / or groups which comprise an initiator for CMRP;(h) groups which comprise a CTA for iodine-transfer polymerization (ITP) and / or groups which comprise an initiator for ITP; or(i) groups which comprise an initiator for copper-based reversible-deactivation radical polymerization (Cu-based RDRP) and / or groups which comprise a CTA for Cu-based RDRP.

5. A polymer according to any one of the preceding claims wherein the groups for controlling SI RDRP are:(a) groups which comprise an initiator for ATRP, selected from groups comprising any one of thewhereinR1is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl, heteroaryl and ester;R2is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;X1is Br or Cl;each of R3, R4and R5independently is hydrogen or an unsubstituted or substituted group selected from C O alkyl, aryl and heteroaryl;X2is Br, Cl or I, and is preferably Br or Cl;each of R42and R52independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;each of R6and R7independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;X3is Br, Cl or I, and is preferably Br or Cl;each of R62and R72independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;R8is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; andX4is Br or Cl; or(b) groups which comprise a CTA or initiator for RAFT polymerisation, selected from groups comprising any one of the following moieties:whereinZ is -CH2O-, -CH2N(RV)-, O or N(RV) wherein Rvis hydrogen or an unsubstituted or substituted group selected from C O alkyl, aryl and heteroaryl;Ar1is an unsubstituted or substituted group selected from aryl and heteroaryl;R10is unsubstituted or substituted C1-20 alkyl;each of R11, R12, R13and R14independently is hydrogen or an unsubstituted or substituted group selected from C O alkyl, aryl and heteroaryl;Ar2is an unsubstituted or substituted group selected from aryl and heteroaryl;LRis unsubstituted or substituted C1-20 alkylene, which C1-20 alkylene is optionally interrupted by O, OC(O) or N(R”)C(O) wherein R” is H, CM alkyl or aryl;RRis unsubstituted or substituted C1-20 alkyl;Lsis unsubstituted or substituted C1-20 alkylene;each of Ruand RTindependently is an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; andAr3is an unsubstituted or substituted group selected from aryl and heteroaryl; or(c) groups which comprise an initiator for photoiniferter-mediated polymerisation (PIMP), selected from groups comprising any one of the following moieties:whereinLRis unsubstituted or substituted C1-20 alkylene, which C1-20 alkylene is optionally interrupted by O, OC(O) or N(R”)C(O) wherein R” is H, CM alkyl or aryl;each of Ruand RTindependently is an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;Z is -CH2O-, -CH2N(RV)-, O or N(RV) wherein Rvis hydrogen or an unsubstituted or substituted group selected from C O alkyl, aryl and heteroaryl;Lsis unsubstituted or substituted C1-20 alkylene;each of R15and R16independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; andeach of R17and R18independently is an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; or(d) groups which comprise an initiator for Cu-based RDRP and / or groups which comprise a CTA for Cu-based RDRP, selected from groups comprising any one of the following moieties :whereinR1is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl, heteroaryl and ester;R2is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;X1is Br or Cl;each of R3, R4and R5independently is hydrogen or an unsubstituted or substituted group selected from C O alkyl, aryl and heteroaryl;X2is Br, Cl or I, and is preferably Br or Cl;each of R42and R52independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;each of R6and R7independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;X3is Br, Cl or I, and is preferably Br or Cl;each of R62and R72independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;R8is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; andX4is Br or Cl.

6. A polymer according to any one of the preceding claims wherein the groups for controlling SIRDRP are:(a) groups which comprise an initiator for ATRP, selected from groups which comprise any one of the following moieties:(b) groups which comprise a CTA or initiator for RAFT polymerisation, selected from groups which comprise any one of the following moieties:(c) groups which comprise an initiator for photoiniferter-mediated polymerisation (PIMP), selected from groups which comprise any one of the following moieties:

7. A polymer according to any one of the preceding claims which comprises a polymer backbone, wherein the reactive intermediate precursor groups are within the polymer backbone or are covalently bonded to the polymer backbone.

8. A polymer according claim 7 wherein the reactive intermediate precursor groups are covalently bonded to the polymer backbone.

9. A polymer according to claim 8 wherein each group for controlling SIRDRP is independently either covalently bonded to one of the reactive intermediate precursor groups or covalently bonded to the polymer backbone.

10. A polymer according to claim 9 wherein each group for controlling SIRDRP is covalently bonded to one of the reactive intermediate precursor groups.

11. A polymer according to any one of the preceding claims wherein the reactive intermediate precursor groups are carbene precursor groups selected from hydrazone groups of formula (A), diazo groups of formula (B) and diazirine groups of formula (C):wherein R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-e alkyl group or an unsubstituted or substituted aryl group.

12. A polymer according to any one of the preceding claims wherein the reactive intermediate precursor groups are carbene precursor groups selected from hydrazone groups of formula (A)wherein R1is H or -S(O)2R2, and R2is an unsubstituted or substituted C1-6 alkyl group or an unsubstituted or substituted aryl group, optionally wherein R1is a tosyl group.

13. A polymer according to claim 11 or claim 12 wherein the polymer comprises n groups of formula (I)whereinn is as defined in claim 1;each E, which is the same or different, is one of said carbene precursor groups;each L, which is the same or different, is a single bond or a linker group; andeach R, which is the same or different, is a group comprising at least one of said groups for controlling SIRDRP.

14. A polymer according to claim 13 wherein each L, which is the same or different, is a single bond or a linker group of formula (XII)wherein:A1is bonded to E, wherein A1is bonded to the carbon atom bonded to R, wherein A1is: a single bond or an unsubstituted or substituted group selected from arylene, heteroarylene, Ci-20 perfluoroalkylene, *-0-Ci-2o alkylene, *-0-Ci-2o perfluoroalkylene, *-O-arylene, *-O-heteroarylene, *-N(R”)-CI-2O alkylene, *-N(R”)-CI-2O perfluoroalkylene, *-N(R”)-arylene, *-N(R”)-heteroarylene, *-S-Ci-2o alkylene, *-S-Ci-2o perfluoroalkylene, *-S-arylene, *-S-heteroarylene, *-C(R’)2-CI-2O alkylene, *-C(R’)2-CI-2O perfluoroalkylene, *-C(R’)2-arylene, *-C(R’)2-heteroarylene and Ci-20 alkylene, wherein each R’ is independently selected from a halogen atom, CMO haloalkyl, C O fluoroalkyl, CMO perfluoroalkyl, aryl, heteroaryl, C3-10 carbocyclyl, Cs-ioheterocyclyl, tri(Ci-ioalkyl)silyl, aryldi(Ci-io alkyl)silyl, diaryl(Ci-io alkyl)silyl, triarylsilyl, C2-10 alkenyl, C2-10 alkynyl and Ci-10 alkyl, wherein * is the point of attachment of A1to E, wherein each of said C1-20 alkylene and C1-20 perfluoroalkylene groups is optionally interrupted by N(R”), O, S or arylene, and wherein R” is independently selected from H, Ci e alkyl and aryl;A2is a single bond or an unsubstituted or substituted group selected from C1-20 alkylene, C1-20 perfluoroalkylene, arylene, heteroarylene, *-Ci-2o alkylene-(0-Ci-2o alkylene-)mwherein m is 1 to 20, *-Z1-Ci-2o alkylene, *-Z1-Ci-2o perfluoroalkylene, *-Z’-arylene, *-Z’ -heteroarylene and *-Z1-Ci-2o alkylene-(0-Ci-2o alkylene-)mwherein m is 1 to 20, wherein Z1is selected from O, S, C(O), S(O), S(O)2, N(R”), C(O)O, OC(O), C(O)N(R”) and N(R”)C(O), wherein * is the point of attachment of A2to A1, wherein each of said C1-20 alkylene and C1-20 perfluoroalkylene groups is optionally interrupted by N(R”), O, S or arylene, and wherein each R” is independently selected from H, Ci-e alkyl and aryl; andA3is a single bond or an unsubstituted or substituted group selected from *-Z2-arylene, *-Z2-heteroarylene, *-Z2-CI-2O alkylene, arylene, heteroarylene, C1-20 alkylene, *-Z2-arylene-O, *-Z2-heteroarylene-O, *-Z2-CI-2O alkylene-O, *-arylene-O, *-heteroarylene-O, *-Ci-2o alkylene-O, C(O), S(O)2, *-OC(O), *-N(R”)C(O), O, S, N(R”), *-C(O)O, *-C(O)N(R”), *-S(O)2O, C120 alkenylene, Ci.20 alkynylene, *-Z2-CI-2O alkenylene and *-Z2-CI-2O alkynylene, wherein Z2is selected from O, S, N(R”), C(O), S(O), S(O)2, C(O)O, OC(O), C(O)N(R”) and N(R”)C(O), wherein each R” is independently selected from H, Ci-e alkyl and aryl, and wherein * is the point of attachment of A3to A2;wherein at least one of A1, A2and A3is not a single bond, optionally wherein A1is not a single bond.

15. A polymer according to claim 13 or claim 14 wherein each R is a group of formula-ArR-(SpR)P-RRwherein:ArRis an unsubstituted or substituted group selected from arylene and heteroarylene, wherein ArRis bonded to E;SpRis a spacer group;p is 0 or 1; andRRis a said group for controlling SIRDRP,optionally wherein:ArRis unsubstituted phenylene; and / orSpRis unsubstituted or substituted C1-20 alkylene, C1-20 perfluoroalkylene, arylene, heteroarylene or -C1-20 alkylene-(0-Ci-2o alkylene-)mwherein m is 1 to 50, wherein each of said C1-20alkylene and C1-20 perfluoroalkylene groups is optionally interrupted by N(R”), O, S or arylene, and wherein each R”is independently selected from H, Ci-e alkyl and aryl, or SpRis a group of formula (XII) as defined in claim 14 provided that A1in the group of formula (XII) is bonded to Ar*, and A3in the group of formula (XII) is bonded to RR.

16. A polymer according to claim 13 or claim 14 wherein each R is a substituted aryl group or a substituted heteroaryl group, which substituted aryl or heteroaryl group is, or comprises, one of said groups for controlling SIRDRP.

17. A polymer according to claim 13 or claim 14 wherein each R is a substituted phenyl group, which substituted phenyl group is, or comprises, one of said groups for controlling SIRDRP.

18. A polymer according to any one of claims 11 to 17 wherein the n groups of formula (I) are:n groups of formula (la)wherein:n is as defined in claim 1;A is an aryl or heteroaryl ring which is bonded to E and X;each E, which is the same or different, is one of said carbene precursor groups; and each L, which is the same or different, is as defined in claim 12 or claim 13;or n groups of formula (lb)wherein:n is as defined in claim 1;each E, which is the same or different, is one of said carbene precursor groups; and each L, which is the same or different, is a single bond or a phenylene group;wherein, in formula (la) or (lb):(a) each X is selected from any one of the following groups:whereinR1is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl, heteroaryl and ester;R2is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;X1is Br or Cl;each of R3, R4and R5independently is hydrogen or an unsubstituted or substituted group selected from C O alkyl, aryl and heteroaryl;X2is Br, Cl or I, and is preferably Br or Cl;each of R42and R52independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;each of R6and R7independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;X3is Br, Cl or I, and is preferably Br or Cl;each of R62and R72independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;R8is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; andX4is Br or Cl; or(b) each X is selected from any one of the following groups:whereinZ is -CH2O-, -CH2N(RV)-, O or N(RV) wherein Rvis hydrogen or an unsubstituted or substituted group selected from Ci-w alkyl, aryl and heteroaryl;Ar1is an unsubstituted or substituted group selected from aryl and heteroaryl;R10is unsubstituted or substituted C1-20 alkyl;each of R11, R12, R13and R14independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;Ar2is an unsubstituted or substituted group selected from aryl and heteroaryl;LRis unsubstituted or substituted C1-20 alkylene, which C1-20 alkylene is optionally interrupted by O, OC(O) or N(R”)C(O) wherein R” is H, CM alkyl or aryl;RRis unsubstituted or substituted C1-20 alkyl;Lsis unsubstituted or substituted C1-20 alkylene;each of Ruand RTindependently is an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; andAr3is an unsubstituted or substituted group selected from aryl and heteroaryl; or(c) each X is selected from any one of the following groups:whereinLRis unsubstituted or substituted C1-20 alkylene, which C1-20 alkylene is optionally interrupted by O, OC(O) or N(R”)C(O) wherein R” is H, Ci-e alkyl or aryl;each of Ruand RTindependently is an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;Z is -CH2O-, -CH2N(RV)-, O or N(RV) wherein Rvis hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl;Lsis unsubstituted or substituted C1-20 alkylene;each of R15and R16independently is hydrogen or an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl; andeach of R17and R18independently is an unsubstituted or substituted group selected from CMO alkyl, aryl and heteroaryl.

19. A polymer according to claim 18 wherein, in formula (la) or (lb):(a) each X is selected from any one of the following groups:(b) each X is selected from any one of the following groups:(c) each X is the following group:

20. A polymer according to any one of claims 13 to 19 wherein the polymer comprises a polymer backbone, wherein L, in each of said groups of formula (I), (la) or (lb), is bonded to said polymer backbone.

21. A polymer according to any one of claims 7 to 10 and 20 wherein the polymer backbone is a linear or branched polymer or copolymer, optionally wherein the polymer backbone comprises polystyrene or polyethylenimine (PEI), optionally wherein the PEI is branched PEI or hyper-branched PEI.

22. A polymer according to any one of claims 13 to 20 wherein the polymer comprises repeat units of formula (II)whereineach Y is a group of formula (I) as defined as defined in any one of claims 13 to 16, or a group of formula (la) or (lb) as defined in claim 17 or claim 18,optionally wherein the number of repeat units of formula (Up) in the polymer is n, and optionally wherein the polymer further comprises repeat units of formula (IIIp)(IIIp).

23. A process for producing a treated substrate, which treated substrate has a surface suitable for surface -initiated reversible-deactivation radical polymerization (SIRDRP), which process comprises:(a) contacting a surface of a substrate with a polymer for treating a surface, wherein the polymer for treating a surface comprises:n reactive intermediate precursor groups, wherein n is an integer equal to or greater than 3; and m groups for controlling SIRDRP, wherein m is an integer equal to or greater than 3, wherein: the groups for controlling SIRDRP are selected from groups which comprise an initiator and groups which comprise a chain transfer agent (CTA); andthe reactive intermediate precursor groups are selected from carbene precursor groups and nitrene precursor groups, wherein the carbene precursor groups are selected from hydrazone groups offormula (A), diazo groups of formula (B) and diazirine groups of formula (C), and the nitrene precursor groups are azide groups of formula (D):wherein R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-e alkyl group or an unsubstituted or substituted aryl group; and(b) generating carbene or nitrene reactive intermediate groups from the reactive intermediate precursor groups, so that the carbene or nitrene reactive intermediate groups react with the surface of the substrate.

24. A process according to claim 23 wherein the carbene or nitrene reactive intermediate groups react with the surface of the substrate and with the polymer to crosslink the polymer and to bond the polymer to the surface of the substrate.

25. A process according to claim 23 or claim 24 wherein (b) generating carbene or nitrene reactive intermediate groups from the reactive intermediate precursor groups comprises heating the polymer or irradiating the polymer,optionally wherein the process further comprises (bl) washing the treated substrate.

26. A process according to any one of claims 23 to 25 wherein the polymer for treating a surface is as further defined in any one of claims 2 to 22.

27. A process according to any one of claims 23 to 26 wherein the substrate is a porous material or a particle, optionally wherein the porous material is a filter or a membrane.

28. A process according to any one of claims 23 to 27 which further comprises:(c) exposing the surface suitable for surface-initiated reversible -deactivation radical polymerization to one or more monomers, and polymerising the one or monomers on the surface by surface -initiated reversible-deactivation radical polymerization.

29. A process according to any one of claims 23 to 27 which further comprises:(c) exposing the surface suitable for surface-initiated reversible -deactivation radical polymerization to one or more monomers, disposing a covering layer on said surface, andpolymerising the one or monomers on the surface and under the covering layer by surface -initiated reversible-deactivation radical polymerization, optionally wherein the covering layer is a glass layer.

30. A process according to claim 28 or 29 wherein the one or more monomers comprise a monomer which comprises an ionic group, optionally wherein the ionic group is a sulfonic acid group or a salt thereof.

31. A treated substrate which is obtainable by a process as defined in any one of claims 23 to 30.

32. A treated substrate having a surface suitable for surface-initiated reversible-deactivation radical polymerization (SIRDRP), wherein the treated substrate comprises:(a) a substrate; and(b) a reacted polymer disposed on a surface of the substrate,wherein the reacted polymer is obtainable by generating carbene or nitrene reactive intermediate groups from reactive intermediate precursor groups of a polymer for treating a surface, so that the carbene or nitrene reactive intermediate groups react with said surface of the substrate, wherein the polymer for treating a surface comprises n of said reactive intermediate precursor groups, wherein n is an integer equal to or greater than 3, and m groups for controlling SIRDRP, wherein m is an integer equal to or greater than 3, wherein:the groups for controlling SIRDRP are selected from groups which comprise an initiator and groups which comprise a chain transfer agent (CTA); andthe reactive intermediate precursor groups are selected from carbene precursor groups and nitrene precursor groups, wherein the carbene precursor groups are selected from hydrazone groups of formula (A), diazo groups of formula (B) and diazirine groups of formula (C), and the nitrene precursor groups are azide groups of formula (D):wherein R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-6 alkyl group or an unsubstituted or substituted aryl group.

33. A treated substrate which comprises:(a) a substrate;(b) a reacted polymer disposed on a surface of the substrate; and(c) a further polymer, grown by surface -initiated reversible-deactivation radical polymerization (SIRDRP), bonded to the reacted polymer (b),wherein the reacted polymer is obtainable by generating carbene or nitrene reactive intermediate groups from reactive intermediate precursor groups of a polymer for treating a surface, so that the carbene or nitrene reactive intermediate groups react with said surface of the substrate, wherein the polymer for treating a surface comprises n of said reactive intermediate precursor groups, wherein n is an integer equal to or greater than 3, and m groups for controlling SIRDRP, wherein m is an integer equal to or greater than 3, wherein:the groups for controlling SIRDRP are selected from groups which comprise an initiator and groups which comprise a chain transfer agent (CTA); andthe reactive intermediate precursor groups are selected from carbene precursor groups and nitrene precursor groups, wherein the carbene precursor groups are selected from hydrazone groups of formula (A), diazo groups of formula (B) and diazirine groups of formula (C), and the nitrene precursor groups are azide groups of formula (D):wherein R1is H or -S(O)2R2, and R2is an unsubstituted or substituted Ci-e alkyl group or an unsubstituted or substituted aryl group,and wherein the further polymer, grown by SIRDRP, is obtainable by exposing the reacted polymer (b) to one or more monomers, and polymerising the one or monomers by surface -initiated reversible-deactivation radical polymerization.

34. A treated substrate according to claim 33 wherein the further polymer, grown by SIRDRP, comprises ionic groups, optionally wherein the ionic groups include a sulfonic acid group or a salt thereof.

35. A treated substrate according to any one of claims 32 to 34 wherein the polymer for treating a surface is as defined in any one of claims 2 to 22.

36. A treated substrate according to any one of claims 32 to 35 wherein the substrate is a porous material or a particle, optionally wherein the porous material is a filter or a membrane.

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