Iron-catalyzed surface polymer formation

Abstract

The present disclosure relates to iron (Fe) catalysts and their use in surface polymer formations.

Description

[0001] Attorney Docket No. RAD-OIOWO

[0002] IRON- CATALYZED SURFACE POLYMER FORMATION

[0003] Cross-Reference to Related Applications

[0004] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 706,225, titled “Iron-Catalyzed Surface Polymer Formation”, filed October 11, 2024, the entire contents of which are incorporated by reference herein.

[0005] Field

[0006] Disclosed herein are iron (Fe) catalysts and their use in surface polymer formations.

[0007] Background

[0008] Forming polymeric structures on surfaces have become increasingly important in many technologies and applications. “Surface polymers”, “surface bound polymers” or “polymers on a surface” all describe a polymeric structure having polymer chains that are chemically bonded to a surface at one end through covalently bound polymerization initiators. Two methods, known by persons skilled in the art, can be used to achieve such polymeric structure, namely the “grafting to”-approach and the “grafting from”-approach (see Fig. 1 and Fig. 2). In the “grafting to”- approach (Fig. 1), polymers are pre-prepared in solution and then deposited onto the surface in question, since the pre-prepared polymers are designed in such a way that one of the chain-ends has some affinity for the surface of interest. Upon contact with the surface of interest, the polymers will self-assemble on said surface forming surface bound polymers. In the “grafting from”- approach (Fig. 2), small molecules capable of acting as polymerization initiators are covalently bound to the surface of interest in a pre-polymerization step. Subsequently, polymerization is initiated via the polymerization initiators bonded on the surface. Accordingly, surface polymers are formed from the surface monomer-by-monomer.

[0009] While the “grafting to” approach allows for simple preparation procedures and detailed characterization, in that one can prepare the polymers using conventional polymerization methods that can maintain the bonding-to-surface property at the one end of the pre-formed polymer, before initiating the self-assembly procedure, the “grafting to”-approach lacks the ability to form high density surface bound polymeric structures nor flexibility in polymer structures, composition, etc. Main equilibrium conformation of long polymeric structures in solution is a contracted, or a coiled polymer chain, unless the polymer solution is extremely diluted with highly solvating solvent or

[0010] IPTS / 200142442.1 T other means employed to stabilize extended conformation (e.g., pH for ionic polymers). Such extra means to stabilize extended polymer chain conformation may complicate and interfere with the “grafting to” process conditions and make the approach less practical. Therefore, the self-assembly process is being halted by the steric repulsion between the coils of pre-made polymer chains as they self-assemble on the surface leading to loosely packed polymer coils on the surface (see Fig. 1). The “grafting from”-approach allows for the formation of highly dense surface bound polymer structures, as the small initiating molecules can form a much more densely packed layer on the surface (compared to large polymer molecules, see Fig. 2). Such a densely packed layer of initiating molecules is guiding monomer molecule-by-monomer molecule formation of polymer chains, where the extended conformation of growing polymer chains is sterically stabilized by their close proximity to each other. As such, the surface bound polymer structure formed by a “grafting from” approach results in a much higher density of polymer chains. Additionally, as the “grafting from”-approach allows for highly dense surface bound polymer structures, a brush-like structure can be achieved, thus, the name “polymer brush”. In these structures, the polymers are stretched and forced to stand upright due to the steric repulsion between neighbouring polymers creating a unique structure known by people skilled in the art as a “polymer brush” structure. On surfaces, these structures are tethered / attached, usually covalently, at one end to the surface, typically to a solid or semisolid surface, thereby differing from polymers formed in solution and subsequently deposited onto a surface.

[0011] As mentioned above, surface polymers are prepared by one of the following two main strategies: “grafting to” or “grafting from”. In the “grafting to”-approach, polymer chains are deposited onto the surface in question. The “grafting to”-approach suffers from several drawbacks and limitations making it difficult to produce thick and dense surface polymers. In the “grafting fronf’-approach, the surface polymer growth (surface polymer chain propagation, extension of the chain by monomer units) is initiated from initiator-functionalized surfaces, using, for example, a controlled / ”living” polymerization technique, such as anionic polymerization, cationic polymerization, ring-opening polymerization, and controlled radical polymerization.

[0012] Surface polymers within the present context are, thus, polymeric structures having polymer chains that are chemically bonded to a surface at one end via polymerization initiators. Such polymers may be tailored to provide specific chemical and / or physical properties and may produce precisely tailored chemical structures on a molecular scale. They may be used, for example, for storing

[0013] IPTS / 200142442.1 certain chemical species, controlling transport properties, improving surface stability and properties, creating an interface in which dissimilar materials can bind or interact, and other functions. Surface polymers may subsequently join otherwise incompatible materials such as metals and plastics and improve adhesion between such otherwise incompatible materials (see, e.g., WO 2014 / 075695 Al).

[0014] Different polymerization techniques have facilitated the specific design and synthesis of surface polymers with strict molecular control and desired properties. In particular, the surface polymers can be viewed as nanoscale “building blocks” with a wide range of uses, varying from redox activity to biocompatibility and surface alteration, and due to the flexibility of the surface polymers, highly tailored thin films of surface polymers can be created with respect to chemical composition, thickness, density and architecture.

[0015] The various polymerization techniques use a catalyst to initiate surface polymerization. Cu catalysts have been studied widely in the field of surface polymers and polymerizations. In some applications, it could be beneficial to catalysts not being a Cu-based catalyst to achieve higher control of polymerization or specifically to avoid Cu impurities in the resulting surface polymer film. Accordingly, there is a need for the development of alternative catalysts.

[0016] Summary

[0017] In an aspect of the present disclosure, a method for forming surface polymers on a substrate is provided, the method comprising providing a substrate having polymerization initiators on at least a portion of a surface of the substrate, exposing the substrate to a reaction composition comprising a monomer, a catalyst / ligand complex formed from a Fe compound and a ligand, a catalyst activator, and a solvent, to form surface polymers via the polymerization initiators on the substrate. The Fe compound may be a ferric compound or a ferrous compound. The Fe compound may be FeCh, FeBrs, Fe2(SC>4)3, FeCh, FeBr2, or FeSCh. The solvent may be aqueous or a hydrate. The solvent may be a combination of methanol and water, ethanol and water, or isopropanol and water. The catalyst activator may be selected from sodium ascorbate (NaAsc), ascorbic acid (Asc), hydrazine, hydrazine hydrate, sodium thiosulfate, sodium sulfite, sodium dithionite, glucose with GOX, and / or pyrogallic acid. The reaction composition may comprise a buffer and / or a zwitterionic buffer. The buffer may be selected from carbonate buffer, glycine buffer, citrate buffer, phosphate buffer, acetate buffer, ammonium buffer (ammonium chloride / ammonia), formate buffer, and / or

[0018] IPTS / 200142442.1 sodium ascorbate / ascorbic acid buffer. The zwitterionic buffer may be a Good’s buffer selected from MES, PIPES, MOPS, HEPES, CHES, CAPSO and / or CAPS. The ligand may be a nitrogencontaining ligand. The ligand may be a heterocyclic nitrogen-containing ligand. The ligand may be selected from A,A,A’,A”,A”’-pentamethyldiethylene-triamine (PMDETA), tris[2- (dimethylamino)ethyl] amine (MegTREN), tris(2-aminoethyl)amine (TREN), tris(2- pyridylmethyl) amine (TPMA), 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA), tetramethylethylenediamine (TMEDA), 1,4, 8,1 l-tetramethyl-1,4,8,11 -tetraazacyclotetradecane (Me4Cyclam), 2,2’ -bipyridyl (BiPy), and / or pyridine. The monomer may be selected from methyl methacrylate (MMA), methacrylate (MA), allyl methacrylate (AMA), glycidyl methacrylate (GMA), hydroxyethyl methacrylate (HEMA), N-hydroxyethyl acrylamide (HEAM), 2- hydroxyethyl acrylate (HEA), tert-butyl acrylate (tBA), styrene, vinylimidazole (VI), N- vinylpyrrolidone, and vinylpyridine (VPY). In an embodiment, the Fe compound may be FeCh (anhydrous or hydrate).

[0019] In an aspect of the present disclosure, a method for forming a surface polymer on a substrate is provided, the method comprising providing a substrate, exposing at least a portion of the surface of the substrate to a polymerization initiator, and exposing the substrate to a reaction composition comprising a monomer, a catalyst / ligand complex formed from a Fe compound and a ligand, a catalyst activator, and a solvent. The Fe compound may be a ferric compound or a ferrous compound (anhydrous or hydrate). The Fe compound may be FeCh, FeBr?, Fei / SC , FeCh, FeBr , or FeSCU. The Fe compound may be FeCh. The solvent may be aqueous. The solvent may be a combination of methanol and water, ethanol and water, or isopropanol and water. The catalyst activator may be selected from sodium ascorbate (NaAsc), ascorbic acid (Asc), hydrazine, hydrazine hydrate, sodium thiosulfate, sodium sulfite, sodium dithionite, glucose with GOX, and / or pyrogallic acid. The reaction composition may comprise a buffer and / or a zwitterionic buffer. The buffer may be selected from carbonate buffer, glycine buffer, citrate buffer, phosphate buffer, acetate buffer, ammonium buffer (ammonium chloride / ammonia), formate buffer, and / or sodium ascorbate / ascorbic acid buffer. The zwitterionic buffer may be a Good’s buffer selected from MES, PIPES, MOPS, HEPES, CHES, CAPSO and / or CAPS. The ligand may be a nitrogen-containing ligand. The ligand may be a heterocyclic nitrogen-containing ligand. The ligand may be selected from V, V’,V”,A”’-pentamethyldiethylene-triamine (PMDETA), tris[2- (dimethylamino)ethyl] amine (MegTREN), tris(2-aminoethyl)amine (TREN), tris(2- pyridylmethyl) amine (TPMA), 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA),

[0020] IPTS / 200142442.1 tetramethylethylenediamine (TMEDA), 1 ,4,8, 1 l-tetramethyl-1,4,8,11 -tetraazacyclotetradecane (Me4Cyclam), 2,2’ -bipyridyl (BiPy), and / or pyridine. The monomer may be selected from methyl methacrylate (MMA), methacrylate (MA), allyl methacrylate (AMA), glycidyl methacrylate (GMA), hydroxyethyl methacrylate (HEMA), N-hydroxyethyl acrylamide (HEAM), 2- hydroxyethyl acrylate (HEA), tert-butyl acrylate (tBA), styrene, vinylimidazole (VI), N- vinylpyrrolidone, and vinylpyridine (VPY). The Fe compound may be FeCh (anhydrous or hydrate). The method may be operable on a system, the system comprising a polymerization initiator container containing a polymerization initiator agent, wherein the substrate displacement device is configured to bring the portion of the substrate for attachment of polymerization initiators into contact with the polymerization initiator agent to form polymerization initiators at the substrate surface, prior to bringing the portion of the polymerization initiator-modified substrate into contact with the reaction composition, a reaction composition container containing the reaction composition, and a substrate displacement device for bringing at least a portion of a polymerization initiator-modified substrate into contact with the reaction composition in the reaction composition container for a controlled time, wherein the controlled time is sufficient for surface polymers of a specified average dry film thickness to be formed on the portion of the polymerization initiator-modified substrate. The substrate displacement device of the system may comprise any one of a conveyor system, a programmable mechanical arm, or a roll-to-roll mechanism. The system may comprise one or more cleaning containers, each cleaning container containing a cleaning agent, wherein the substrate displacement device is configured to bring the portion of the polymerization initiator-modified substrate into contact with the cleaning agent held by the one or more cleaning containers prior to, or subsequent to, bringing the portion of the polymerization initiator-modified substrate into contact with the reaction composition, or wherein the substrate displacement device is configured to bring the portion of substrate into contact with the cleaning agent held by the one or more cleaning containers prior to, or subsequent to, bringing the portion of the substrate into contact with the polymerization initiator. The polymerization initiator container may be a vacuum oven.

[0021] In an aspect of the present disclosure, a system for forming surface polymers on a substrate, the system comprising a reaction composition container containing a reaction composition, said reaction composition comprising a monomer, a catalyst / ligand complex formed from a Fe compound and a ligand, and a catalyst activator, and a substrate displacement device for bringing at least a portion of a polymerization initiator-modified substrate into contact with the reaction

[0022] IPTS / 200142442.1 composition in the reaction composition container for a controlled time, wherein the controlled time is sufficient for surface polymers to be formed on the portion of the polymerization initiator- modified substrate. The substrate displacement device may comprise any one of a conveyor system, a programmable mechanical arm, or a roll-to-roll mechanism. The system may further comprise a polymerization initiator container containing a polymerization initiator agent, wherein the substrate displacement device may be configured to bring the at least a portion of the substrate for attachment of polymerization initiators into contact with the polymerization initiator agent to form polymerization initiators at the substrate surface, prior to bringing the at least a portion of the polymerization initiator-modified substrate into contact with the reaction composition. The polymerization initiator container is a vacuum oven. The system may comprise one or more cleaning containers, the cleaning containers containing cleaning agents, wherein the substrate displacement device is configured to bring the at least a portion of the polymerization initiator- modified substrate into contact with the cleaning agents of the one or more cleaning containers prior to, or subsequent to, bringing the at least a portion of the polymerization initiator-modified substrate into contact with the reaction composition, and / or the substrate displacement device is configured to bring the at least a portion of substrate into contact with the cleaning agents in the one or more cleaning agents prior to, or subsequent to, bringing the at least a portion of the substrate into contact with the polymerization initiator. The system may further comprise a container for pre- wetting the at least a portion of the substrate prior to bringing the at least a portion of the substrate into contact with the reaction composition. The system may further comprise a reaction composition management system. The reaction composition management system may comprise one or more sensors in relation to the reaction composition container. The sensors may be to measure the pH of the reaction composition and / or the molecular oxygen concentration in the reaction composition. The system may further comprise one or more flow control devices. The one or flow control devices may be selected from circulation pumps, flow guidance grids, filters, and / or mechanical stirring means. The system may further comprise a heating device for annealing the substrate prior to, or subsequent to, bringing the at least a portion of the polymerization initiator-modified substrate into contact with the reaction composition.

[0023] In some instances, a reaction composition may be provided, the reaction composition comprising a monomer, a catalyst / ligand complex formed from a Fe compound and a ligand, a catalyst activator, and a solvent. The Fe compound may be a ferric compound or a ferrous compound. The Fe compound may be FeCh, FeBri, Fe2(SO4)3, FeCh, FeBr2, or FeSO4. The solvent may be

[0024] IPTS / 200142442.1 aqueous. The solvent may be a combination of methanol and water, ethanol and water, or isopropanol and water. The catalyst activator may be selected from sodium ascorbate (NaAsc), ascorbic acid (Asc), hydrazine, hydrazine hydrate, sodium thiosulfate, sodium sulfite, sodium dithionite, glucose with GOX, and / or pyrogallic acid. The reaction composition may comprise a buffer, and / or a zwitterionic buffer. The buffer may be selected from carbonate buffer, glycine buffer, citrate buffer, phosphate buffer, acetate buffer, ammonium buffer (ammonium chloride / am- monia), formate buffer, and / or sodium ascorbate / ascorbic acid buffer. The zwitterionic buffer may be a Good’s buffer selected from MES, PIPES, MOPS, HEPES, CHES, CAPSO and / or CAPS. The ligand may be a nitrogen-containing ligand. The ligand may be a heterocyclic nitrogencontaining ligand. The ligand may be selected from N,N, N’, A”, / V”!-pentamethyldiethylenc- triamine (PMDETA), tris[2-(dimethylamino)ethyl]amine (MeeTREN), tris(2-aminoethyl)amine (TREN), tris(2-pyridylmethyl)amine (TPMA), 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA), tetramethylethylenediamine (TMEDA), 1 ,4,8, 11 -tetramethyl- 1 ,4,8, 11 -tetraazacyclo- tetradecane (Me4Cyclam), 2,2 ’-bipyridyl (BiPy), and / or pyridine. The monomer may be selected from methyl methacrylate (MMA), methacrylate (MA), allyl methacrylate (AMA), glycidyl methacrylate (GMA), hydroxyethyl methacrylate (HEMA), N-hydroxy ethyl acrylamide (HEAM), 2-hydroxyethyl acrylate (HEA), tert-butyl acrylate (tBA), styrene, vinylimidazole (VI), N- vinylpyrrolidone, and vinylpyridine (VPY). The Fe compound may be FeCh (anhydrous or hydrate).

[0025] In some instances, a polymer formed on at least a portion of at least a surface of a substrate may be provided, the polymer being formed by providing a substrate, exposing at least a portion of the surface of the substrate to a polymerization initiator, and exposing the substrate to a reaction composition comprising a monomer, a catalyst / ligand complex formed from a Fe compound and a ligand, a catalyst activator, and a solvent. The Fe compound may be a ferric compound or a ferrous compound (anhydrous or hydrate). The Fe compound may be FeCh, FeBr<, Fe2(SO4)3, FeCh, FeBr2, or FeSO4- The solvent may be aqueous. The solvent may be a combination of methanol and water, ethanol and water, or isopropanol and water. The catalyst activator may be selected from sodium ascorbate (NaAsc), ascorbic acid (Asc), hydrazine, hydrazine hydrate, sodium thiosulfate, sodium sulfite, sodium di thionite, glucose with GOX, and / or pyrogallic acid. The reaction composition may comprise a buffer. The buffer may be selected from carbonate buffer, glycine buffer, citrate buffer, phosphate buffer, acetate buffer, ammonium buffer (ammonium chloride / ammonia), formate buffer, and / or sodium ascorbate / ascorbic acid buffer.

[0026] IPTS / 200142442.1 The zwitterionic buffer may be a Good’s buffer selected from MES, PIPES, MOPS, HEPES, CHES, CAPSO and / or CAPS. The ligand may be a nitrogen-containing ligand. The ligand may be a heterocyclic nitrogen-containing ligand. The ligand may be selected from N,N,N’,N”,N”,- pentamethyldiethylene-triamine (PMDETA), tris[2-(dimethylamino)ethyl]amine (MeeTREN), tris(2-aminoethyl)amine (TREN), tris(2-pyridylmethyl)amine (TPMA), 1,1,4,7,10,10- hexamethyltriethylenetetramine (HMTETA), tetramethylethylenediamine (TMEDA), 1,4,8,11- tetramethyl- 1,4,8, 11 -tetraazacyclotetradecane (Me4Cyclam), 2,2 ’-bipyridyl (BiPy), and / or pyridine. The monomer may be selected from methyl methacrylate (MMA), methacrylate (MA), allyl methacrylate (AMA), glycidyl methacrylate (GMA), hydroxyethyl methacrylate (HEMA), N-hydroxyethyl acrylamide (HEAM), 2-hydroxyethyl acrylate (HEA), tert-butyl acrylate (tBA), styrene, vinylimidazole (VI), N-vinylpyrrolidone, and vinylpyridine (VPY). The Fe compound may be FeCh (anhydrous or hydrate).

[0027] Description of the drawings

[0028] Certain embodiments of the matter disclosed herein are illustrated in the accompanying drawings. The drawings are, however, in no way intended to limit the scope of the disclosure. In the drawings:

[0029] Fig. 1 illustrates the “grafting to” principle.

[0030] Fig. 2 illustrates the “grafting from” principle.

[0031] Fig. 3 schematically illustrates the principle of grafting density of polymerization initiators to “dummy” initiators (non-polymerization initiators) where the polymerization initiator is diluted with the “dummy” initiator. From left to right: the polymerization initiator is present with a higher density (o). Right: no “dummy” initiator present.

[0032] Fig. 4 shows a plot of surface polymer average dry film thickness as a function of reaction time for 3 different kinds of monomers: MMA, GMA, and HEMA, see Example 5.

[0033] Fig. 5 shows a plot of surface polymer average dry film thickness (y-axis) as a function of polymerization time (x-axis) for a PMMA polymer forming reaction with and without the use of buffer, see Example 6.

[0034] Fig. 6 shows a plot of surface polymer average dry film thickness (y-axis) as a function of polymerization time (x-axis), see Example 7.

[0035] Fig. 7 shows a plot of surface polymer average dry film thickness (y-axis) as a function of polymerization time (x-axis), see Example 7.

[0036] IPTS / 200142442.1 Fig. 8 shows a plot of surface polymer average dry film thickness (y-axis) as a function of polymerization time (x-axis), see Example 8.

[0037] Fig. 9 shows a plot of surface polymer average dry film thickness (y-axis) as a function of polymerization time (x-axis), see example 9.

[0038] Fig. 10 shows a plot of surface polymer average dry film thickness (y-axis) as a function of polymerization time (x-axis), see Example 10.

[0039] Fig. 11 shows a plot of surface polymer average dry film thickness (y-axis) as a function of polymerization time (x-axis), see Example 11.

[0040] Fig. 12 shows a plot of surface polymer average dry film thickness (y-axis) as a function of polymerization time (x-axis), see Example 12.

[0041] Fig. 13 is a schematic illustration of a system for forming surface polymers on at least a portion of a substrate applying the methods disclosed herein.

[0042] Fig. 14 is a schematic illustration of an exemplary substrate displacement device, the substrate displacement device comprising a roll-to-roll processing device.

[0043] Detailed description

[0044] In an aspect of the present disclosure, an iron (Fe) catalyst is provided. The iron catalyst may be useful for catalyzing the formation of surface polymers from polymerization initiators present on at least a portion of a surface of a substrate.

[0045] Thus, the present disclosure relates to methods for forming surface polymers using the iron (Fe) catalyst as described herein. The iron (Fe) catalyst catalyzes the formation of surface polymers from polymerization initiator-sites on at least a portion of the substrate.

[0046] Herein, the terms “iron” and “Fe” may be used interchangeably. Herein, “iron catalyst” and “Fe catalyst” may be used interchangeably. Herein, “iron compound” and “Fe compound” may be used interchangeably.

[0047] In an aspect of the present disclosure, a method for forming surface polymers on a substrate is provided, the method comprising providing a substrate having polymerization initiators on at least a portion of a surface of the substrate, exposing the substrate to a reaction composition to form surface polymers via the polymerization initiators on the substrate, the reaction composition

[0048] IPTS / 200142442.1 comprising a monomer, a catalyst / ligand complex formed from an iron (Fe) compound and a ligand, a catalyst activator, and a solvent.

[0049] In the reaction composition, the “catalyst / ligand formed from an iron (Fe) compound and a ligand” may be present as the catalyst / ligand preformed from the iron (Fe) compound and the ligand, or be present as the iron (Fe) compound and the ligand. By way of example, a solution of the Fe compound and the ligand may be prepared and a certain amount added to the reaction composition together with the other components. By way of example, all components of the reaction composition may be mixed, in any order, including the Fe compound and the ligand.

[0050] In some aspects, the method for forming a surface polymer on a substrate involves providing a substrate, exposing the substrate to a polymerization initiator, and exposing the substrate to a reaction composition comprising a monomer, a catalyst / ligand complex formed from a Fe compound and a ligand, and a solvent, to form the surface polymer from the polymerization initiators present on at least a portion of the surface of the substrate.

[0051] Within the present context, the expression “a portion of the surface” is intended to mean that a surface of the substrate may have one or more areas with polymerization initiators. A substrate may have one or more surfaces, and each surface may comprise one or more areas with polymerization initiators.

[0052] The Fe compound (catalyst) concentration in the reaction composition may be in the range 0.001- 1 mM. The concentration of catalyst in the reaction composition may be in the range 0.02-0.32 mM, for example in the range 0.02 mM, 0.04 mM, 0.08 mM, 0.16 mM, or 0.32 mM.

[0053] The iron compound may be provided either as a ferric or ferrous compound (anhydrous or hydrate). The term “ferric” is intended to mean Fe in oxidation state III, i.e., Fe(III). The term “ferrous” is intended to mean Fe in oxidation state II, i.e., Fe(II). Examples of ferric compounds include, but are not limited to FeCh, FeBn, and Fe2(SO4)3. Examples of ferrous compounds include, but are not limited to, FeCh, FeBr2, and FeSCU.

[0054] In accordance with the above, a method for forming surface polymers on a substrate may be provided, the method comprising providing a substrate having polymerization initiators on at least

[0055] IPTS / 200142442.1 a portion of a surface of the substrate, exposing the substrate to a reaction composition comprising a monomer, a catalyst / ligand complex formed from FeCh and a ligand, a catalyst activator, and a solvent, to form surface polymers via the polymerization initiators on the substrate.

[0056] In some instances, the method comprises providing a substrate, exposing the substrate to a polymerization initiator, and exposing the substrate to a reaction composition comprising a monomer, a catalyst / ligand complex formed from FeCh and a ligand, and a solvent. Exposing the substrate to a polymerization initiator covalently attaches the polymerization initiator to the surface of the substrate.

[0057] Surface polymers may then be formed from the polymerization initiators attached to at least a portion of a surface of the substrate.

[0058] Attachment of polymerization initiators to a surface of a substrate, from which surface polymers may be propagated, may be performed by various procedures. Polymerization initiators are covalently bonded to the surface of the material, see, e.g., WO 2014 / 0075695. The polymerization initiators may be provided with a predefined chemistry to enable attachment onto the surface of the substrate, depending on the nature of the substrate. Non-limiting examples of suitable chemistries for attaching polymerization initiators on surfaces include but are not limited to: aryl diazonium salts, organosilanes, organothiols, organophosphonic acids, organophosphonates, catechols, iodonium salts, alkenes, alkynes, and sol-gel coatings. Surface anchored polymerization initiators can be prepared as multilayer films or monolayer films. Monolayer films can be densely packed (full monolayer coverage) or partly packed, covering all or only a part of the available surface. The density of the polymerization initiator influences the density and may possibly influence the growth rate of the subsequently formed surface polymer. Density of polymerization initiators would be understood by persons of ordinary skill as the number of polymerization initiators per unit area of the substrate.

[0059] The attachment of polymerization initiators usually follows a l-step or a 2-step process. The 1- step process applies grafting of benzyl halide (like benzyl chloride) or secondary or tertiary halide moieties onto the surface of the substrate either by diazonium or silane grafting. The benzyl halide and secondary and tertiary halide moiety act as the polymerization initiator for the following surface-initiated polymerization. The 2-step process usually applies surface grafting of an initial

[0060] IPTS / 200142442.1 organic compound with a nucleophilic group, and in a second step using the nucleophilic group to attach an initiator moiety. The nucleophilic group may include a hydroxyl or amine group. Then, the nucleophilic group may be reacted with an electrophile to add an initiator moiety, forming a covalent bond between the two. The initiator moiety may be, e.g., benzyl halide and tertiary halide moieties.

[0061] The attachment process is further described below. The procedures may in general apply to all types of substrates. Prior to attachment of polymerization initiators to form the polymerization initiator layer, the surface of the substrate may be cleaned using various techniques, including sonication in ammonia, ABC-clean A200, a solution of DI-water:NH3:H2O2 (5:1 :1), acetone, and / or water, to mention some. In some instances, the substrates are subjected to the polymerization initiator forming process without any prior cleaning steps. Following attachment of polymerization initiators, the substrate may be rinsed and / or annealed at ambient conditions or at elevated temperatures.

[0062] Silane grafting 1-step:

[0063] Polymerization initiators may be attached to a surface in one step by silane grafting of trialkoxysilane with benzyl halide or tertiary halide groups. The silane grafting may be done by vapor deposition, in solution, by spray coating, or paint-on coating.

[0064] Diazonium grafting 1-step:

[0065] Polymerization initiators may be attached to a surface in one step by grafting aryl diazonium salts with benzyl halide groups. The diazonium grafting may be done either by activating the aryl diazonium salt electrochemically or chemically or by letting it react spontaneously. Diazonium salts may be pre-synthesized before being used for grafting reaction or formed in-situ during grafting reaction from a set of precursors added to the grafting reaction solution.

[0066] Diazonium grafting 2-step:

[0067] Another route of polymerization initiator attachment is by a two-step process. The first step being grafting of an aryl diazonium salt that contains a nucleophilic group (alcohol or amine). In a second step, a nucleophilic acyl substitution reaction adds a halogen containing group, giving the attached polymerization initiator.

[0068] IPTS / 200142442.1 Silane grafting 2-step:

[0069] The first step being grafting of a silane that contains a nucleophilic group (alcohol or amine). In a second step, a nucleophilic acyl substitution reaction adds a halogen containing group, giving the attached polymerization initiator.

[0070] Other processes for forming the polymerization initiator layer may be applied.

[0071] An example of a polymerization initiator is p-(chloromethyl)phenyltrimethoxysilane (CPTMS) which may be attached using a vapor deposition method or a dipping method. Another example is a-bromobutyryl bromide (BiBB). Another example is the polymerization initiator -(chloro- methyl)phenyltrimethoxysilane (CPTMS) in combination with a “dummy” initiator phenyltrimethoxysilane (PTMS) or (3-glycidyloxypropyl)trimethoxysilane (GPTMS), the latter which display an epoxy (epoxide) group suited for further modification by ring-opening of the epoxy (epoxide) group. Within the present context, the term “dummy initiator”, “non-polymerization initiator” or “initiator not initiating polymerization” is a chemical entity which does not initiate surface polymer formation in the presence of an active polymerization catalyst.

[0072] Thus, the presence of polymerization initiators in the polymerization initiator layer may be “diluted” by the simultaneous presence of “dummy” initiators to form a polymerization initiator layer containing polymerization initiators active for surface polymer formation and chemical entities (the “dummy” initiator) not active for surface polymer formation. The “dummy” initiator may be added in a certain percentage together with the polymerization initiator, thus, competing with the polymerization initiator about available attachment sites on the substrate surface. Dilution of the polymerization initiator with a “dummy” initiator may be used to adjust the density of the polymerization initiators on the surface of the substrate, thus, aiding in controlling density (“grafting density”, i.e. the number of surface polymer chains per unit area of the substrate) of subsequently formed surface polymers. Here “grafting” means monomer-by-monomer propagation of surface polymers from the polymerization initiators. The density of the initiators (both polymerization initiators and non-polymerization / ”dummy” initiators) influences the density of the subsequently formed surface polymer propagated from the polymerization initiator sites. As mentioned above, the density of polymerization initiators is intended to mean the number of polymerization initiators per unit area. Non-limiting examples of suitable percentage ratios (molecular- % (mol%) of polymerization initiator to non-polymerization initiator) may be in the

[0073] IPTS / 200142442.1 range 100:0 (no non-polymerization initiator), 90:10, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 20:80, and 10:90. The principle of adjusting the grafting density of polymerizations with “dummy” initiators is shown schematically in Fig. 3. Fig. 3 shows a varying dilution of the polymerization initiator with a non-polymerization initiator (“dummy” initiator). Fig. 3 is not intended to be an exact representation of the grafting density nor the distribution of the polymerization initiators as compared to the “dummy” initiators. In Fig. 3, “right” schematically shows the polymerization initiator is present at all available sites, i.e. no “dummy” polymerization initiator present. In Fig. 3, “middle” and “left” schematically shows increasing presence of “dummy” initiators, with the “left” image showing a higher presence of “dummy” initiators as compared to the “middle” image.

[0074] It is expected that a wide range of different substrates will be useful in connection with the disclosure herein, however, suited substrates should provide a surface, allowing firstly attachment of first polymerization initiators, and secondly formation of surface polymers of first polymer molecules from said first polymerization initiator sites. Substrates may wholly or partly be composed of metal (like aluminum, steel, nickel, gold, silver, platinum, chrome, copper, iron and alloys), glass, carbon, graphite, graphene, carbon black, monoclays, ceramics, composite materials, plastics, polymer materials, semiconductors, compound semiconductors (e.g., gallium arsenide (GaAs), gallium nitride (GaN), germanium sulfide (GeS), and indium phosphide (InP)), and particles (e.g., Si, metal, metal alloys and coated particles). Substrates may be patterned or unpattemed. If patterned, substrate surface(s) may comprise one or more of the mentioned substrate materials. The substrate may be composed of several layers of different materials, optionally being attached together, e.g., using a glue, or be a blend of different materials. The substrate may have any size, shape and structure, including an elongated structure, and may be in the form of pieces, threads, fibers, cables, wires, hollow structures, particles, nanoparticles, monolayers etc. Particles and nanoparticles may be uncoated or coated with another material and may further be in the form of aggregates (multiple (nano)particles forming an assembly of individual (nano)particles). Aggregates may in some cases be viewed as one (nano)particle. Substrates may also be composed of one or more of the above mentioned, e.g., the substrate may be a base material comprising glass, silicon, GaAs, GaN, GeS, InP, dielectric material, ceramic, composite, as well as layered and patterned structures thereof. Substrates may have any form and shape, be elongated, be hollow, have protrusions or recesses, etc.

[0075] IPTS / 200142442.1 A portion or portions of a substrate may be “masked” so as to only attach polymerization initiators to unmasked areas on the substrate. Different techniques may be used to accomplish such specific attachment of polymerization initiators. For example, the portion or portions of the substrate may be covered by a film or layer during polymerization initiator attachment. Alternatively, contact between a portion or portions of a substrate and the reaction composition for forming surface polymer may be limited by, e.g., a masking with for example a film or a layer covering the portion or portions of the substrate on which surface polymers are not to be formed, or by immersing, into the reaction composition, only those portions of the substrate onto which surface polymers are to be formed. In general, any masking should be non-reactive with other chemistries to which the substrate is exposed and should be easily removable from the substrate.

[0076] Different polymerization techniques have facilitated the specific design and synthesis of surface polymers with strict molecular control and desired properties. In particular, the surface polymers can be viewed as nanoscale “building blocks” with a wide range of uses, varying from redox activity to biocompatibility and surface alteration, and due to the flexibility of the surface polymers, highly tailored thin films of surface polymers can be created with respect to chemical composition, thickness, density and architecture.

[0077] Several methods for forming surface polymers are known, among them SI- ATRP (surface-initiated atom transfer radical polymerization), SI- RAFT (surface- initiated reversible-addition fragmentation chain transfer), SI-NMP (surface-initiated nitroxide-mediated polymerization), SIPIMP (surface-initiated photoiniferter-mediated polymerization), and SI-A(R)GET (surface- initiated activators (regenerated) by electron transfer) ATRP. A review is given in Chem. Rev. 2009, 109, 5437-5527. Other approaches include SET-LRP (single-electron transfer living radical polymerization) and SARA ATRP (supplemental activator and reducing agent atom transfer radical polymerization).

[0078] When forming surface polymers, polymerization initiators are firstly formed on the surface or portion(s) of the surface onto which the surface polymers are to be formed. Secondly, the surface or portion(s) of the surface is brought into contact with suitable monomers, catalysts, ligands and optionally a solvent, or suitable monomers, catalyst, ligands, a reducing agent and optionally a solvent, whereby the surface polymer can form using certain reaction conditions. The polymerization initiators and the monomers are chosen so as to suit the purposes and properties of the

[0079] IPTS / 200142442.1 resulting surface polymers. Surface polymers may also be formed as layers of surface polymers by repeating the polymeric architecture, e.g., using another starting monomer (so-called block copolymers).

[0080] Among these known procedures for formation of surface polymers, (ARGET) ATRP and SET- LRP are widely used. For the polymerizing chains to propagate, a monomer, a catalyst, a ligand and a solvent are needed. In (ARGET) ATRP and SET-LRP polymerizations, some reactions activate the catalyst, thereby, promoting polymerization, and at the same time, other reactions deactivate the catalyst to impede polymerization. SARA-ATRP and SET-LRP are described, e.g., in https: / / www.cmu.edu / maty / atrp-how / procedures-for-initiation-of-ATRP / SARA-ATRP-or- SET-LRP.html.

[0081] Both the SET-LRP and (ARGET) ATRP method rely on the formation of a complex between the ligand and a halide formed with a transition metal as specified in the Periodic Table (usually CuCh or CuBri in the case of ARGET ATRP, and Cu(0) in the case of SET-LRP, but other transition metals and halogens may be used).

[0082] The ARGET ATRP involves a halogen transfer between a dormant halogen capped species, Pn-X and Cu(I)X / L catalyst, resulting in the formation of a propagating radical (Pnradical) and Cu(II)X2. The propagating radical undergoes polymerization with monomers, forming the growing polymer chain. Controlling the ratio between Cu(I)X / L and Cu(II)X2 / L in ARGET ATRP allows control of the polymerization itself.

[0083] From WO 2019 / 196999 Al, which is incorporated by reference in its entirety, as if fully set forth herein, an alternative oxygen-tolerant method for forming surface polymers is disclosed. The catalyst / ligand complex described in WO 2019 / 196999 Al is halogen free in so far as the catalyst / ligand complex formed is not complexed with a halogen anion as the catalyst / ligand complex formed is a catalyst oxide. An advantage is that the complex (pre-)formed between the transition metal and the ligand is inactive (i.e., not available for initiating polymerization of the monomer) and furthermore stable (oxygen-insensitive), but the system can be activated “on demand” by a reducing agent / catalyst activator, thus, initiating polymerization and propagation of the surface polymers.

[0084] IPTS / 200142442.1 The iron (Fe) compounds disclosed herein offer an alternative to the generally applied Cu- containing catalysts. The catalysts based on iron (Fe) compounds may be useful in applications, where Cu-containing catalysts may be less desirable. In some instances, the iron (Fe) compounds may provide a polymerization rate and profile different from conventionally used Cu-containing catalysts, thus, providing polymerization control beneficial for some applications.

[0085] In accordance with the methods disclosed herein, the substrate including one or more surfaces of the substrate, or portions of one or more surfaces of the substrate may be brought into contact with the reaction composition for surface polymer formation. It is understood that the surfaces or portions of the surfaces of the substrate may have been subjected to attachment of polymerization initiators prior to contact with the reaction composition. It is to be understood that the components of the reaction composition may be mixed and subsequently be brought into contact with the substrate. In some instances, the components of the reaction composition may be prepared as discrete compositions and mixed prior to or following contact with the substrate. E.g., the monomer may be prepared as a discrete component (solvated in the solvent if needed), and the catalyst / ligand complex may be brought into contact with the catalyst activator, whereafter the activated catalyst / ligand complex may be brought into contact with the substrate, followed by addition of the monomer. E.g., the monomer, the catalyst / ligand complex, and the solvent may be brought into contact with the substrate, and the catalyst activator may be dissolved in the solvent and subsequently be added. E.g., the monomer, the catalyst / complex, the solvent, and the catalyst activator may be pre-mixed, and subsequently be brought into contact with the substrate.

[0086] For forming surface polymers, the substrate and the reaction composition as defined herein are typically kept in contact with each other for a suitable time period (residence time or polymerization time), sufficiently to form surface polymers essentially having an average dry film thickness within a desired range. The polymerization time may be as long as needed. Suited polymerization times include, but is not limited to, up to 24 hours, e.g., 2 seconds, 5 seconds, 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 5 minutes, 30 minutes, 1 hour, 2 hours, 3 hours, 4 hours and 5 hours. For a manufacturing perspective, polymerization times between 20 seconds and 20 minutes may often be suitable. The surface polymer formation may take place at ambient temperature (room temperature), or with cooling or heating. Suitable temperatures include, but are not limited to, such from 5°C up to 120°C, such as from room temperature (approximately 20°C) to 120°C. Specific temperatures include, but are not limited to,

[0087] IPTS / 200142442.1 5°C, 10°C, 15°C, 20°C, room / ambient temperature (approximately 20°C), 30°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, and 120°C. The polymerization time and temperature during the polymerization time may suitably be computer controlled. Following formation of surface polymers, the substrate may be subjected to optionally multiple rinsing and cleaning processes, typically involving flushing with a suitable solvent, sonicating, and / or drying at room temperature or elevated temperature (“annealing”).

[0088] It is to be understood that by the term “thickness of a surface polymer” or “thickness of a polymer on a surface” is meant the surface polymer film formed on the substrate, i.e., the surface polymer as defined herein. The thickness is often measured as the dry film thickness by ellipsometry but may be measured by other means such as reflectometry or by measuring a step edge in the coating by atomic force microscopy, or profilometry. To determine the dry film thickness, several ellipsometry measurements are taken in evenly spaced positions on the substrate surface. At a beam incidence angle of 65° the beam spot of the ellipsometer, i.e., the area from which each measurement collects data for the thickness calculation, is approximately 0.16 cm2. E.g., for a 2” silicon wafer quadrant substrate (total area of -20.3 cm2), different data collection routines may include 10, 45, or more measurement spots, meaning that the area from which thickness data is collected ranges from 1.6 cm2to 7.2 cm2or more, corresponding to thickness data being obtained from 7.8 % to 35.5 % of the total surface area. Adding more measurement points to the measurement routine would mean that average dry film thickness data would be obtained from a larger fraction of the surface area, although the inventors generally find that the good homogeneity of the surface polymers presented herein may suffice for determining the average dry film thickness of a surface polymer. Generally speaking, a substrate with a surface polymer film may be considered dry when no visible solvent film, droplets, or residues are observed, by visual inspection, on the surface of the substrate. Measurements such as atomic force microscopy and profilometry demand that a step edge is made in the coating from the outer edge of the coating and all the way to the surface of the substrate, by e.g. scratching. In the dry state, the surface-tethered polymer molecules acquire a conformation between fully collapsed and stretched conformation where the degree of stretching depends on the grafting density.

[0089] The iron (Fe)-catalyzed surface polymer formation offers control of the polymerization and the obtained average dry film thickness of the surface polymers. The polymerization time influences the obtained average dry film of the surface polymer, however, with the iron (Fe) catalysts

[0090] IPTS / 200142442.1 disclosed herein surface polymers of a desired average dry film thickness may easily be controlled. In some instances, the average dry film thickness of the surface polymer may be up to approximately 500 nm. In some instances, the average dry film thickness of the surface polymer may be up to approximately 250 nm. In some instances, the average dry film thickness of the surface polymer may be up to approximately 150 nm. In some instances, the average dry film thickness of the surface polymer may be up to approximately 130 nm. In some instances, the average dry film thickness of the surface polymer may be up to approximately 100 nm. In some instances, the average dry film thickness of the surface polymer may be up to approximately 75 nm. In some instances, the average dry film thickness of the surface polymer may be up to approximately 50 nm or less. In some instances, the average dry film thickness may be up to approximately 10 nm. Here, the term “approximately” is intended to be within ± 20% of the stated average dry film thickness. In some instances, the “approximate” may be within ± 10%, ± 5% or less. It has been shown herein (Examples) that the polymerization can be controlled so as to yield surface polymers within the mentioned thicknesses.

[0091] For forming surface polymers, the solvent of the reaction composition may be aqueous. Thus, the solvent may be a mixture of water and an organic solvent. The water and the organic solvent may be miscible with each other. Suitable solvents include, but are not limited to, alcohols, dipolar aprotic solvents (for example, tetrahydrofuran, methyl acetate, ethyl acetate, butyl acetate, dimethyl sulfoxide, dimethyl formamide), methylene carbonate, ethylene carbonate, propylene carbonate, ethyl lactate alcohol, toluene, ionic liquids, and supercritical CO2. The solvent may be chosen so as to provide sufficient solubility and / or miscibility of the components of the reaction composition. The ratio (volume-% (vol%)) between water and organic solvent may be 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, or 90: 10 as well as range therebetween.

[0092] The solvent may be a combination of water and methanol, water and ethanol, or water and isopropanol. The solvent may be a combination of water and methanol, ethanol, and / or isopropanol.

[0093] The solvent may solubilize the other components of the reaction composition. Some of the components may be solubilized in the solvent prior to the surface polymer formation and mixed with the remaining components. Thus, any of the monomer, the catalyst and the ligand, and the catalyst activator may be solubilized in the solvent prior to surface polymer formation. Non-

[0094] IPTS / 200142442.1 limiting ways of mixing include: mixing of catalyst, ligand and solvent prior to mixing with catalyst activator optionally solubilized in solvent, or mixing of catalyst, ligand, solvent, and catalyst activator prior to addition of monomer optionally solubilized in solvent, or mixing of catalyst, ligand, solvent, and monomer prior to addition of catalyst activator solubilized in solvent. It is to be understood that “solvent” in the aforementioned cases may include water alone, or a mixture of water and organic solvent. Other ways of mixing of the components of the reaction composition may be envisaged, and, thus, the order of mixing of the components should not be restricted to the disclosure of the Examples.

[0095] The Fe compound and the ligand form a complex. The catalyst activator reduces the iron of the catalyst / ligand complex to yield a polymerization active catalyst / ligand complex. The activation of the complex formed between the Fe compound and the ligand may take some time, and is believed to depend, e.g., on the Fe compound, the ligand used, and the pH of the reaction composition. A beneficial property of the iron (Fe) catalyst is that the catalyst as applied in the methods disclosed herein is sufficiently oxygen insensitive to make possible polymerization under atmospheric conditions as opposed to a sealed environment (confined space, under argon or nitrogen purging). Thus, the methods described herein may be such wherein the surface polymer formation takes place at atmospheric conditions. As opposed to the conventional sealed environment, the methods disclosed herein make possible high- volume manufacturing (HVM).

[0096] Suited catalyst activators include, but is not limited to, sodium ascorbate (NaAsc), ascorbic acid (Asc), hydrazine, hydrazine hydrate, sodium thiosulfate, sodium sulfite, sodium dithionite, glycose, glucose with GOX(glycose with oxidizing enzyme), and / or pyrogallic acid. The catalyst activator may be used in excess compared to the catalyst. Excess catalyst activator may, e.g., be 10-500 times. The catalyst activator is responsible for the turnover between oxidized deactivating and / or activating catalyst states (i.e. Fe(ITI) and Fe(IT), respectively). It is presently believed that the principal reaction pathway for catalyst activation is reduction; that is, the catalyst activator may be a species capable of reducing the catalyst of the complex formed between the catalyst and the ligand from its inactive state to its catalytically active state, where surface polymer formation can take place.

[0097] In some embodiments, the reaction composition may comprise a buffer, and / or a zwitterionic buffer. It is hypothesized that a buffer may stabilize the complex formed between the Fe compound

[0098] IPTS / 200142442.1 and the ligand to control surface polymerization. The inventors speculate that the buffer may to some extend result in the formation of Fe(OH)3, the formation of which may aid in catalyzing the polymerization. The terms “buffer” and ’’zwitterionic buffer” are defined herein as an agent which, when added to the reaction composition, can within a certain pH range withstand changes in pH when acidic or alkaline substances / components are added to the reaction composition or is formed in the reaction composition. Buffer systems include combinations of a weak acid and its conjugate base, or a weak base and its conjugate acid. Buffers may suitably be prepared as an aqueous solution but may in some cases involve adding a non-aqueous solution or solid / semi-solid formulation to the reaction composition.

[0099] Non-limiting examples of buffers are carbonate buffer, glycine buffer, citrate buffer, phosphate buffer, acetate buffer, ammonium buffer (ammonium chloride / ammonia), formate buffer, and / or sodium ascorbate / ascorbic acid buffer. Non-limiting examples of zwitterionic buffers are a Good’ s buffer selected from MES, PIPES, MOPS, HEPES, CHES, CAPSO and / or CAPS.

[0100] The ligand to be applied in the methods described here may be a nitrogen-containing ligand. In some embodiments, the ligand may be a heterocyclic nitrogen-containing ligand. Non-limiting examples include A, A^’, / V”,A”’-pentamethyldiethylene-triamine (PMDETA), tris[2-(dimethyl- amino)ethyl]amine (MeeTREN), tris(2-aminoethyl)amine (TREN), tris(2-pyridylmethyl)amine (TPMA), 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA), tetramethylethylenediamine (TMEDA), 1, 4, 8, 1 1 -tetramethyl- 1,4, 8,11 -tetraazacyclotetradecane (Me4Cyclam), 2,2’-bipyridyl (BiPy), and / or pyridine. Pyridine derivatives may also be suited ligands. The amount of ligand in the reaction composition may suitably be defined as a ratio to the concentration of catalyst in the reaction composition. The ratio of ligand to catalyst in the reaction composition may be in the range 0.001 : 1 to 1000: 1. The ratio of ligand to catalyst in the reaction composition may, in some embodiments, be in the range 0.005:1 to 100:1 , for example 0.13:1 , 0.5:1 , 1.0:1 , 2.0: 1 , .5:1 , 7.5: 1 or 12:1. In general, an excess amount of ligand as compared to amount of catalyst may be used.

[0101] The reaction composition may in some cases comprise a halide compound for increasing the “livingness” of the polymerization. A “living” polymerization refers to a polymerization where the rate of termination is minor in comparison to the rate of propagation of polymer molecules from the polymerization initiators. As a result, living polymerizations show a more linear relationship between surface polymer chain length and time. The halide compound to be used

[0102] IPTS / 200142442.1 1 herein is a compound capable of providing a halide anion. Non-limiting examples of such compounds are NaCl, NaBr, KC1, KBr, MgCh, MgBn, CaCh, HC1, HBr, LiCl, LiBr, CaB , as well as combinations thereof. Halide compounds may disassociate in the reaction composition, generating halide anions which may form complexes with and / or bind to catalysts in solution, resulting in an increased concentration of catalyst / ligand-X (X is the halide anion) complexes which are responsible for end-capping, and thus deactivating, propagating surface polymer chainend radicals to deliver alkyl halides. Consequently, the number of propagating surface polymer chain-end radicals at any given time is lowered, which may result in at least the following effects; (1) a lowering of the rate with which polymer molecules grow initially due to a lower number of propagating chains, and (2) a lowering of the rate with which chain termination between two propagating polymer molecule chain-end radicals occur (through recombination or disproportionation), leading to an increased living character of the polymerization. The halide compound may suitably be used in the range of from 0.1 M to 2 M.

[0103] Surface polymers are formed from monomers present in the reaction composition. Monomer(s) may be chosen to provide compatibility / adhesion / elasticity / hydrophilicity surface properties, as appropriate for a specific application. Monomer(s) can also be selected to enhance or diminish electrical and / or ionic conductivity, surface properties, and / or permeability. Monomers may be chosen to improve interface stability of a surface in question. Furthermore, the introduction of functional groups or combination of functional groups may provide improvement over various desired properties, like density, dielectric constants, diffusion barrier, wettability, etc. Monomers may suitably be used in an amount corresponding to a percentage of the total volume of the reaction composition. For example, a liquid monomer may constitute e.g. 0.5 vol%, 2 vol%, or 10 vol% of a reaction composition. In accordance with the present disclosure, an amount of monomer may be chosen to obtain desired surface polymerization kinetics, solubility of the monomer, and cost of the monomer. The monomer may suitably be used in the range 0.5 vol% to 50 vol%.

[0104] The formation of surface polymers may be performed at ambient temperature, at a temperature above ambient temperature, or at a temperature below ambient temperature. The temperature during surface polymer formation may be controlled automatically. The polymerization time may vary depending on components of the reaction composition, the targeted average dry film thickness of the surface polymers, process optimization, etc.

[0105] IPTS / 200142442.1 Following formation of the surface polymer, the formed surface polymer is indicated with a “P” as prefix to the monomer. By way of example, methyl methacrylate monomer is denoted MMA, and after polymerization, the surface polymer molecule is denoted PMMA. Likewise, 2-hydroxy- ethyl methacrylate is denoted HEMA, and after polymerization, the surface polymer molecule is denoted PHEMA.

[0106] The surface polymer formed may be composed of several types of monomeric units. Such “mixed” surface polymers may be obtained as a result of formation of co-polymers. Co-polymers may be in the form of random co-polymerization (two or more monomers present in a certain ratio), or block co-polymerization (two or more consecutive polymerization events).

[0107] Thus, non-limiting examples of appropriate monomer types include anionic, cationic, zwitterionic, protic and aprotic monomers, and include acrylates, methacrylates, halogen- substituted alkenes, acrylamides, methacrylamides, and styrenes, as well as mixtures thereof. The generic monomer structure comprises a polymerizable part (a vinyl group), which in certain embodiments is connected to a functional group responsible for the specific functionality (e.g., adhesion, permeability, electric and ionic conductivities) of the certain monomer through a certain linker chemistry.

[0108] For acrylate monomers, non- limiting examples of functional moieties include but are not limited to alkyl groups, aryl groups, sulfonates, fluorosulfonates, carboxyls, metal carboxylates, ethers, poly(ether) groups, bis(sulfonyl)amides, fluorinated sulfonates, perfluoroalkyl carboxylate, borate, fluorinated borate, borate ester derivatives, bis(trifluoromethane)sulfonimide, triflimides and derivatives thereof, halogenated alkyl chains, and mono-, di-, and tri-alkoxy silanes.

[0109] The polymerizable part and the functional part of monomer can, in certain embodiments, be connected by a linker moiety. Non- limiting examples of appropriate linker chemistries include but are not limited to alkyl chain, esters, ethers, poly (ethers), amines, amides, aryls, and any combination(s) thereof. Non-limiting examples of appropriate acrylate monomers containing alkyl linkers include but are not limited to methyl acrylate, ethyl acrylate, and lauryl acrylate. Nonlimiting examples of monomers using ether and poly(ether) linker chemistry include but are not limited to poly(ethylene glycol) methyl ether acrylate, and poly(ethylene glycol) acrylate. Non-

[0110] IPTS / 200142442.1 limiting examples of monomers without linker chemistry include but are not limited to acrylic acid, lithium acrylate, sodium acrylate, and vinyl imidazole.

[0111] For methacrylate monomers, non-limiting examples of appropriate functional moieties include but are not limited to carboxylic acids, metal carboxylates, esters, alkyl alcohols, oxiranes (epoxides), linear and branched alkyl groups, alkenes, aryl groups, sulfonates, fluorosulfonates, bis (sulfonyl) amides, fluorinated sulfonates, perfluoroalkyl carboxylate, borate, fluorinated borate, borate ester derivatives, bis(trifluoromethane)sulfonimide, triflimides, and derivatives thereof, halogenated alkyl chains, and mono, di, and tri-alkoxy silanes.

[0112] Non-limiting examples of linker chemistries include but are not limited to alkyl chains, esters, ethers, poly(ethers, amines, amides, aryls, and any combination(s) thereof.

[0113] Non-limiting examples of methacrylate monomers include but are not limited to methacrylic acid, lithium methacrylate, sodium methacrylate, methyl methacrylate (MMA), potassium 3-sulfpropyl methacrylate (K-SPMA), 2-hydroxyethylmethacrylate (HEMA), glycidyl methacrylate (GMA), ethyl methacrylate, n-butyl methacrylate (BuMA), tert-butyl methacrylate (tBMA), lauryl methacrylate, (((perfluorobutyl)sulfonyl)oxy)methyl methacrylate, 3-(N-((trifluoromethyl)- sulfonyl)sulfamoyl)propyl methacrylate, I / / , l / / ,2 / / ,2 / / -heptadecalluorodecyl methacrylate (HFDMA), allyl methacrylate (AMA), 2-((triethoxysilyl)oxy)ethyl methacrylate, and 2-(3- (triethoxysilyl)propyl)ethyl methacrylate.

[0114] Non-limiting examples of acrylate monomers include but are not limited to methyl acrylate (MA), tert-butyl acrylate (tBA), lauryl acrylate (LA), and 2-hydroxyethylacrylate (HEA).

[0115] Non-limiting examples of appropriate halogen-substituted alkene monomers include but are not limited to vinyl chloride, vinylidene difluoride, tetrafluoroethylene, chlorotrifluoroethylene, and hexafluoropropylene.

[0116] Non-limiting examples of appropriate acrylamide monomers include but are not limited to acrylamide, A-zso-propylacrylamide, A-terZ-butylacrylamide, and A-hydroxyethyl acrylamide.

[0117] IPTS / 200142442.1 Non- limiting examples of appropriate methacrylamide monomers include but are not limited to N- Ao-propylmethacrylamide, methyl methacrylamide, A-tert-butylmethacrylamide, and / -hydroxy- ethyl methacrylamide.

[0118] Non-limiting examples of appropriate styrene monomers include but are not limited to styrene, 4- methylstyrene, 2,3,4,5,6-pentafluorostyrene, p-divinylbenzene, 4-chlorostyrene, sodium 4-vinyl- benzenesulfonate, lithium 4-vinylbenzenesulfonate, and 4-vinylphenyl 1, 1,2, 2, 3, 3, 4,4,4- nonafluorobutane- 1 -sulfonate.

[0119] As mentioned above, the surface polymers described herein may also be copolymers. Within the present context, the expression “co-polymer” or “co-polymers” is intended to mean a polymer molecule of the surface polymer as defined herein comprising at least two different monomeric repeat units. Co-polymers may be formed by copolymerizing different types of monomers or by subsequent partial chemical modification of a homopolymer (within the surface polymer) to add a chemical modification of one type of monomeric repeat unit to obtain a different type of monomeric repeat unit. Repeating the steps of the methods described herein multiple times may provide formation of multiple layers of surface polymers (block co-polymers, b-polymers).

[0120] The surface polymer may possess specific properties obtained through block co-polymers, random polymers, or binary mixed polymer, resulting in a surface polymer with a difference in surface polymer architecture. In such embodiments, the different monomers of block co-polymers, random polymers or binary mixed polymers may contribute with different properties resulting in a surface polymer with a combination of desired properties. Also, forming block co-polymers, random polymers or binary mixed polymers may provide an overall thicker surface polymer, i.e. a surface polymer with higher average dry film thickness. Two or more functional groups (e.g., halogen atoms, hydroxyl groups, or amine groups) can be incorporated, resulting in surface polymers with a unique set of combined properties, each of which is inherent from individual monomers. Formation of block co-polymers, and random polymers are usually formed as a result of a “living” polymerization where the formed surface polymer has viable chain-ends that may initiate further polymerization in subsequent polymerization events.

[0121] The “monomer-by -monomer” approach (“grafting from” approach) for formation of surface polymers offers myriads of monomer types and combinations thereof in forming surface polymers

[0122] IPTS / 200142442.1 of desired structure, composition, and properties. The methods presented herein have proven sufficiently oxygen insensitive to make possible the polymerization to generally take place under ambient atmospheric conditions, and this offers a flexibility in the design of surface polymers as well as in the preparation of them, including high-volume manufacturing.

[0123] Surface polymers formed on a substrate may be analyzed, e.g., by ellipsometry according to the following procedure. Ellipsometry provides a measurement of the average dry film thickness of the surface polymer across the substrate or a portion of a substrate. Generally speaking, a substrate with a surface polymer (is herein considered dry when no visible solvent film, droplets, or residues are observed with the naked eye on the surface of the substrate. Other methods of obtaining a dry substrate may be used, some of which include withdrawal of the substrate(s) from the reaction composition, followed by rinsing by sonication in DI- water for 5 minutes, followed by sonication in acetone for 5 minutes, and drying in ambient air 1-30 minutes. In some cases, the substrates may be flushed with acetone after withdrawal from the reaction composition, followed by airdrying in an oven at 80°C for 15 minutes. Still, in some cases, the substrate(s) may be flushed with acetone, then sonicated in acetone for 5 minutes and left to dry at 80°C for 10 minutes. Alternative, the substrate(s) may be flushed with isopropanol (iPrOH), then sonicated in iPrOH for 5 minutes and left to dry under nitrogen flow for 10-30 minutes. Then, the substrate may be subjected to ellipsometry.

[0124] In an aspect of the present disclosure, a reaction composition is provided, the reaction composition comprising a monomer, a catalyst / ligand complex formed from a Fe compound and a ligand, a catalyst activator, and a solvent.

[0125] Upon contact between the reaction composition and a substrate having polymerization initiators on at least a portion of a surface, surface polymers may be formed on the substrate.

[0126] The Fe compound is a ferric compound or a ferrous compound (anhydrous or hydrate). In some instances, the ferric compound may be FeCE, FeB , or Fe2(SO4)3- The ferrous compound may be FeCE, FeBr2, or FeSCU The Fe compound may be FeCE (anhydrous or hydrate).

[0127] Suitable monomers, ligands, catalyst activators, solvents are disclosed above in connection with the methods discussed herein.

[0128] IPTS / 200142442.1 It is to be understood that the reaction composition comprises the individual components mentioned (monomer, catalyst / ligand formed from a Fe compound and a ligand, catalyst activator, and solvent) whether or not the components are already mixed or provided separately for mixing.

[0129] In an aspect of the present disclosure and encompassed within the disclosure, a polymer formed on at least a portion of a substrate is provided. The surface polymer may be formed using the methods and the reaction compositions disclosed herein. The surface polymer may also be formed on a system as disclosed herein, operable according to the methods described herein.

[0130] Thus, a polymer formed on at least a portion of at least a portion of a surface of a substrate may be obtained by providing a substrate, exposing the substrate to a polymerization initiator, and exposing the substrate to a reaction composition comprising a monomer, a catalyst / ligand complex formed from a Fe compound and a ligand, and a solvent.

[0131] In some instances, the Fe compound may be a ferric compound or a ferrous compound (anhydrous or hydrate). Non-limiting examples of ferric compounds are FeCh, FeB . and Fe2(SO4)s. Nonlimiting examples of ferrous compounds FeCh, FeBr2, and FeSO4- In some instances, the Fe compound may be FeCh (anhydrous or hydrate).

[0132] Suited monomers, catalyst / ligand complexes formed from a Fe compound and a ligand, and solvents are described in detail above in connection with the methods and the reaction compositions.

[0133] Fig. 13 is a non-limiting schematic illustration of a system 100 for forming surface polymers on at least a portion of a substrate. The methods described herein may be operable on a system as described in the following. The system 100 comprises a reaction composition container 104, or one or more reaction containers 104, containing the aforementioned reaction composition 105. Container(s) 104 may relate to any vessel or chamber suitable for holding the reaction composition. At least a portion of a polymerization initiator- modified substrate 102 is brought into contact with the reaction composition 105, for example by at least partly immersing a desired surface of substrate 102 into the reaction composition, thereby enabling surface polymers to form on the substrate.

[0134] IPTS / 200142442.1 Optionally, system 100, may comprise one or more further containers, each container comprising different compositions and / or agents for treating the substrate 102, either prior to the substrate being brought into contact with the reaction composition 105, or afterwards. Where substrate 102 has not been pre- treated with a polymerization initiator, then the system 100 may further comprise a container 106 holding a polymerization initiator chemistry 107, thus, forming the polymerization initiator-modified substrate 102 in the container 106. As mentioned above, a portion or portion of substrate 102 may be masked, e.g., by applying a film or a layer, so as to enable attachment of polymerization initiators only to a portion or portions onto which surface polymers are to be formed subsequently.

[0135] When Fig. 13 relates to an embodiment in which the substrate has been pre-modified with a polymerization initiator, a cleaning container (or one or more, i.e., multiple cleaning containers, as needed) 114 may be provided, comprising cleaning agent(s) or cleaning device(s) 116. The cleaning agent / device 116 may be used to clean the surface of substrate 102 prior to bringing it into contact with reaction composition 105 held by the reaction composition container 104. This may be achieved by, at the very least, subjecting at least a portion of the substrate 102 on which it is desired to form surface polymers on, to cleaning procedures in container 114 using cleaning agent / device 116. In this way, any impurities which may interfere with the formation of the surface polymers, are removed from the surface of substrate 102, prior to bringing substrate 102 into contact with the reaction composition 105. System 100 may additionally include a substrate displacement device 103 for bringing the substrate 102 at least partly into contact with the reaction composition 105 held by the reaction composition container 104 for a controlled time to ensure surface polymers form. The expression “at least partly” is intended to mean that a portion or portions of substrate 102 is brought into contact with the reaction composition 105. The displacement device 103 may be configured to control the contact between substrate 102 and reaction composition 105. Alternatively, as mentioned above, the portion or portions of substrate 102 may be covered (“masked”) by, e.g., a film or a layer suited for avoiding contact between reaction composition 105 and the substrate 102. The displacement device 103 may be used to remove the substrate 102 from the reaction composition 105 following surface polymer formation. Thus, the substrate displacement device 103 may be configured to maintain the surface of substrate 102 at least partly in contact with the reaction composition 105 to enable surface polymers to form on at least a portion of the surface of the substrate, and the substrate displacement device 103 may

[0136] IPTS / 200142442.1 be configured to maintain the substrate 102 in contact with the reaction composition 105 for a predetermined amount of time.

[0137] In instances where the system 100 may comprise two or more containers, such as illustrated in Fig. 13, in addition to bringing substate 102 into contact with the compositions contained by each container, the substrate displacement device 103 may be configured to transport substrate 102 to and from each container. For example, as illustrated in Fig. 13, the substrate displacement device 103 may be configured to firstly transport substrate 102 into contact with cleaning agent / device 116 in container 114, and / or a polymerization initiator chemistry 107 if the substrate is not premodified with a polymerization initiator as mentioned previously, held in the container 106, and subsequently to transport the substrate 102 from the container 106 to the reaction composition container 104, where the substrate is brought at least partly into contact with the reaction composition 105 held by the reaction composition container 104. The term “at least partly” is intended to mean that a portion or portions of substrate 102 is brought into contact with the reaction composition 105. Alternatively, as mentioned above, the portion or portions of substrate 102 may be covered (“masked”) by, e.g., a film or a layer suited for avoiding contact between the reaction composition 105 and the substrate 102. In the latter example, the substrate may in embodiments be cleaned between initiator modification and surface polymer formation. In some instances, system 100 may comprise multiple cleaning containers in sequence (not shown).

[0138] System 100 as shown in Fig. 13 may further be equipped with a reaction composition management system (not shown). The reaction composition management system may include one or more sensors in relation to the reaction composition container 104. The one or more sensors may be configured to measure a characteristic of the reaction composition 105, which characteristic may relate to a physical or chemical characteristic of the reaction composition 105, such as the pH of the reaction composition and / or the molecular oxygen concentration in the reaction composition. The sensor data may be used to determine whether a value of the measured characteristic lies within a predetermined threshold for the surface polymer formation process. If the measured characteristic is determined to lie outside the predetermined threshold, then the chemistry of the reaction composition 105 may be adjusted by dispensing different chemistries to reaction composition container 104 to adjust the value of the measured characteristic, e.g., an acidic or an alkaline substance to adjust the pH value of the reaction composition 105 or a substance to control the oxygen concentration of the reaction composition 105. In this way, it is possible to ensure that

[0139] IPTS / 200142442.1 the values of the one or more characteristics of the reaction composition are within a range suitable for forming desired surface polymers on the substrate 102. A control unit operatively connected to the one or more sensors, may be used to control one or more dispensers for dispensing one or more chemistries to control the chemistry of the reaction composition 105.

[0140] Similarly, the chemistry of the reaction composition 105 may be adjusted by dispensing any one or more of the components of the reaction composition into the reaction composition 105. For example, the components may relate to any one or more of: at least one monomer, at least one ligand, at least one catalyst, at least one catalyst activator, and at least one solvent. In some embodiments, the control unit may be configured to output a control signal for controlling operation of a dispenser for dispensing one or more components of the reaction composition into the reaction composition 105, in response to the measured characteristic of the reaction composition 105, or in response to an observed time variance of the characteristic. For example, a value of the measured characteristic may be monitored over a time period using the one or more sensors. The control unit may determine to output a control signal to control operation of one or more dispensers to dispense the one or more components on the basis of an observed variation over time of the measured characteristic. The observed variation may be indicative that the chemistry of the reaction composition 105 is varying such that the surface polymer formation process is falling out of specification - for example, surface polymer formation is reduced and / or compromised. The dispensing of one or more components of the reaction composition into the reaction composition 105 may help to maintain one or more chemical properties of the reaction composition 105, to enable the formation of surface polymers. In some instances, dispensing of the one or more control agents and / or components of the reaction composition may occur periodically. In such embodiments, sensor measurement data may be used to ensure the chemical and / or physical characteristics of the reaction composition 105 are as desired. However, dispensing of the one or more control agents and / or components of the reaction composition, and more specifically the outputting of one or more control signals by the control unit to control the dispensers, may be independent of any specific sensor measurement. (The latter method of maintaining the reaction composition 105 may be based on known rates of consumption of components of the reaction composition or on known variation over time of pH or molecular oxygen concentration, for example.) In yet further embodiments, dispensing of the one or more agents and / or components of the reaction composition, and more specifically the outputting of one or more control signals by the control unit, may be directly dependent on one or more measured

[0141] IPTS / 200142442.1 characteristics of the reaction composition 105. Similarly, the outputting of one or more control signals by the control unit to control dispensing of the one or more control agents and / or components of the reaction composition may be dependent on a measured sensor signal indicative of a change in a measured characteristic of the reaction composition 105. Combinations of some of these different methods may also be advantageous, for example using dispensing of agents and / or components for maintenance of the reaction composition 105 over shorter time intervals without use of sensor measurements, combined with adjustments being made based on regular sensor measurements made at longer time intervals.

[0142] In some instances, it may be advantageous to control the environmental conditions in which the system 100 is implemented, and in particular in which the surface polymers are formed. For example, this may help to reduce contaminants and other impurities contaminating the reaction composition 105 and / or the substrate 102. Non-limiting examples of contaminants and impurities may include bulk polymers or metals. Similarly, controlling environmental conditions such as, but not limited to, pressure, temperature, humidity, and / or inert atmosphere, may be beneficial to the process for forming surface polymers. To achieve this, in some embodiments, system 100 may be implemented in an environmentally controlled chamber. For example, the aforementioned containers may sit within one or more environmentally controlled chambers. In some embodiments all of the containers may sit within one or more chambers. In some embodiments a subset of the containers may sit within one or more chambers. For example, it is envisaged that in some embodiments the polymerization initiator container may sit within a chamber, whilst the reaction composition container 104, may sit outside a chamber. Similarly, in some embodiments it is envisaged that cleaning of the substrate prior to polymerization initiator formation may also occur in an environmentally controlled chamber, in which case the associated cleaning agent container also could sit within an environmentally controlled chamber.

[0143] The substrate displacement device 103 may relate to any device capable of transporting the substrate from one container to another container. For example, the substrate displacement device 103 may relate to a mechanical device. In particular, it is envisaged that the substrate displacement device 103 may comprise any one of: a conveyor system, a programmable mechanical arm or arms, and / or a roll-to-roll processor / mechanism.

[0144] IPTS / 200142442.1 A conveyor system as used herein may refer to a mechanical system that is used to move a material, such as the substrate, which in embodiments may be in a substrate holder on its own or with other substrates, from one process container to another, typically comprising a movable conveyor, powered by a drive system and having a series of rollers or pulleys that support and guide the belt. In use, the substrate may be placed on the conveyor which passes the substrate through the one or more containers comprised in the system. In this way, as the conveyor is powered, the substrate is passed through the component(s) held by each container within the system. Furthermore, in some embodiments the containers are enclosures in which the reaction composition, or other appropriate wet chemistry, is uniformly applied over the substrate using spray nozzles.

[0145] In some instances, a programmable mechanical arm, such as a robotic arm, may be used to transport the substrate, which may be in a holder as described above. The programmable mechanical arm, in embodiments, has the capability to move substrate holders horizontally and vertically in and out of containers and from container to container. The programmable mechanical arm may be equipped with gripping devices comprising suction devices, enabling handling of larger substrates. Such gripping device is, e.g., disclosed in WO 2019 / 114893.

[0146] A roll-to-roll processor or mechanism is particularly advantageous for use where the substrate may be flexible and elongated, such as a cable, wire, foil, sheet or any other elongated flexible substrate. Fig. 14 illustrates such an embodiment, in which the substrate displacement device relates to a roll-to-roll processor 118, comprising a sending roll 121, a receiving roll 122 and a plurality of rollers 120. At least some of the rollers 120 and the receiving roll 122 are driven, thereby enabling a flexible elongated substrate 123 to be passed from the sending roll 121 through the reaction composition 105 in container 104 to the receiving roll 122. The roll-to-roll mechanism can be utilized as a replacement to the substrate displacement device 103 in Fig. 13 when elongated flexible substrates are being processed. In some embodiments, the substrate may be masked in certain areas to form surface polymers only from unmasked polymerization initiator. In some embodiments, polymerization initiator sites may only be attached at certain portion(s) on the substrate as described above. In some embodiments, only the portion(s) of the substrate is immersed into the reaction composition to form surface polymers on the portion(s) of the substrate being in contact with the reaction composition. In some embodiments, forming surface polymers on portion(s) of the substrate may be a combination of masking and bringing only the desired portion(s) of the substrate in contact with the reaction composition. The substrate displacement

[0147] IPTS / 200142442.1 device or another type of substrate displace device may be suited for carrying out the specific contact between the substrate and the reaction composition.

[0148] In yet further embodiments, at least one of the plurality of containers may comprise an annealing oven for annealing the formed surface polymers. In a similar manner as described previously, the substrate displacement device 103 may be configured to transport the substrate with the formed surface polymers to the annealing oven 109 and to bring the substrate with surface polymers into position for annealing. The annealing oven is equipped with a heating device for annealing the formed surface polymers and the gas environment 111 in the oven may be controlled as needed - for example, to avoid oxidation by using only non-oxidizing gases.

[0149] According to some instances, a system for forming surface polymers on a substrate may comprise: a reaction composition container containing a reaction composition, said reaction composition comprising: a monomer, a catalyst and a ligand forming a catalyst / ligand complex, a catalyst activator, and a solvent, and a substrate displacement device for bringing at least a portion of a polymerization initiator-modified substrate into contact with the reaction composition in the reaction composition container for a controlled time, wherein the controlled time is sufficient for surface polymers of a specified average dry film thickness to be formed on the portion of the polymerization initiator-modified substrate. Furthermore, the substrate displacement device may comprise any one of: a conveyor system, a programmable mechanical arm, or a roll-to-roll mechanism. Furthermore, the system may comprise a polymerization initiator container containing a polymerization initiator agent, wherein the substrate displacement device is configured to bring the portion of the substrate for attachment of polymerization initiators into contact with the polymerization initiator agent to form polymerization initiators at the substrate surface, prior to bringing the portion of the polymerization initiator-modified substrate into contact with the reaction composition. Furthermore, the system may comprise one or more cleaning containers, the cleaning containers containing cleaning agents, wherein the substrate displacement device is configured to bring the portion of the polymerization initiator-modified substrate into contact with the cleaning agent prior to, or subsequent to, bringing the portion of the polymerization initiator- modified substrate into contact with the reaction composition, or the substrate displacement device is configured to bring the portion of substrate into contact with the cleaning agent prior to, or subsequent to, bringing the portion of the substrate into contact with the polymerization initiator. Furthermore, extra containers may be added as needed for rinsing, etc. between processes. The

[0150] IPTS / 200142442.1 substrate displacement device may be one or more robots or a conveyor system with the capability to move substrates horizontally and vertically in and out of containers and from container to container. In some embodiments, system 100 may include one or more containers holding a chemistry for pre- wetting the substrate 105 prior to bringing the substrate 105 into contact with the reaction composition 105 in the reaction composition container 104. The pre-wetting chemistry may essentially correspond to the reaction composition 105, however, without the catalyst activator, for example, to pre-wet the surface but not induce polymerization reaction. In some embodiments, the pre-wetting chemistry may include one or more components to enhance prewetting of the substrate 102, for example, a composition of solvent differing from the reaction composition 105, or a pre-wetting agent with a specific pH. In some instances, system 100 may comprise more than one pre-wetting container for wetting the substate prior to or subsequent to any step of the process (or method) running on system 100.

[0151] In some instances, each container of system 100 may include flow control devices, such as, for example, circulation pumps, flow guidance grids, filters, and / or mechanical stirring means. The flow control devices may facilitate distribution of the chemistry in a container around the substrate 102, and may, in some cases, be useful for filtering off potential contaminants.

[0152] Aspects and embodiments of the disclosure are further illustrated by the following, non-limiting examples.

[0153] Examples

[0154] List of chemicals used:

[0155] Throughout the examples, DI- water refers to tap water deionized using the deionizing equipment Silhorko with M22-F softening plant, RO B l -2 Reverse Osmosis plant and Silex 2BS mixed bed plant. The DI- water has a conductivity of <0.5 p S / cm, indicating an ultrapure quality with very low presence of ions, below 0. 1 mg / L. The quality of the DLwater was confirmed at least weekly.

[0156] Silicon wafer substrates (Si), Test CZ-Si wafer, 4 inch, thickness = 525 ± 25 pm, (100), p-type (Boron), were purchased from MicroChemicals GmbH (r = 5.08 cm) and cut into l / 4th of a wafer. Acetone (>99%) was purchased from Chemsolute.

[0157] Isopropanol (iPrOH) was purchased from Chemsolute (99%).

[0158] IPTS / 200142442.1 / ?-(Chloromethyl)phenyltrimethoxysilane (CPTMS) (95%) was purchased from Gelest. Tris(2-pyridylmethyl)amine (TPMA) (98%) was purchased from Tokyo Chemical Industry. FeCh- 6H2O (> 99 %) was purchased from ChemSolute (Batch no. 27.2131106).

[0159] Methyl methacrylate (MMA) (99 %, 30 ppm MEHQ inhibitor) was purchased from Sigma Aldrich (lot no. STBK8834).

[0160] Glycidyl methacrylate (GMA) (> 97 %) was purchased from Sigma Aldrich. rert-Butyl acrylate (tBA) (98%) was purchased from Sigma Aldrich.

[0161] Allyl methacrylate (AMA) (98%) was purchased from Sigma Aldrich Sodium ascorbate (NaAsc) (98%) was purchased from Sigma Aldrich.

[0162] Sodium carbonate (Na2COs) (min 99.8%) was purchased from Chemsolute

[0163] Sodium bicarbonate (NaHCCL). (min 99.7%) was purchased from Chemsolute

[0164] Copper(II)chloride dihydrate (CuC12-2H2O) (99.0%) was purchased from Sigma Aldrich.

[0165] List of premixed solutions:

[0166] IM carbonate buffer: 22 g Na2COs and 153 g NaHCCh was dissolved in 2 L DLwater.

[0167] Fe catalyst solution: 2.6 g TPMA and 0.7 g FeCh-OFLO was dissolved in 250 mL DLwater and 250 mL EtOH and sonicated for 5 minutes.

[0168] List of equipment used in the Examples:

[0169] “Big sonicator” refers to an ULTRASONIC CLEANER PROCLEAN 28.0 from Ulsonix (40 kHz, 480 W).

[0170] “Sonicator” refers toto a Bandelin Sonorex Super RK100 sonicator (35 kHz ultrasound frequency, 80 W nominal ultrasonic power).

[0171] “Vacuum oven” refers to a Faithful Vacuum Drying Oven-DZ-BCII.

[0172] “Oven” refers to a Binder model FD 56.

[0173] Ellipsometry was measured on a J. A. Woollam M-2000 Ellipsometer. This instrument was set to measure 10 points on each substrate, unless otherwise indicated. Each point was analyzed using a Cauchy model providing a thickness and a Mean Square Error (MSE), the latter referring to the goodness of the fit. Thicknesses are thus given as the average of all measured points on the substrate (average dry film thickness). Unless specifically stated otherwise, 10 data points were obtained on each substrate. Standard deviation is the standard deviation based on the entirety of the measured thicknesses. The standard deviation is an estimate of the homogeneity of surface polymers formed. To obtain detailed datasets of surface polymer thickness from which lateral

[0174] IPTS / 200142442.1 maps of surface polymer average dry film thickness can be produced, the ellipsometer instrument can be equipped with focusing optics (J. A. Woollam), reducing the beam spot size (the measured area) from 300 pm x 710 pm to 30 pm x 71 pm at a 65-degree angle of incidence. The much smaller beam size enables measurement of many more points on a substrate, enabling a higher resolution of the surface polymer average dry film thickness.

[0175] Example 1

[0176] Precleaning of substrates prior to deposition of polymerization initiators

[0177] Substrates were precleaned prior to attachment of polymerization initiators. Substrates were generally 14 of a whole Si wafer. The total number of substrates subjected to precleaning may vary (specific number of substrates are indicated in the subsequent examples).

[0178] Racks containing the Si substrates were placed in iPrOH and sonicated for 5 minutes in a big sonicator. Then, the substrates mounted in the racks were placed in an oven at 80°C for 15 minutes. Thereafter, the racks holding the substrates were transferred to a 5: 1:1 DI-water / NfEOH / lECh solution at temperatures between 70°C and 75°C and sonicated for 10 minutes. Next, the rack containing the substrates was flushed under a running tap of Dl-water and transferred to a DI- water container and sonicated for 5 minutes. Finally, the rack holding the substrates was transferred to an iPrOH-containing container and sonicated for 5 minutes, before being dried in an oven at 80°C for 15 minutes.

[0179] Example 2

[0180] Deposition of polymerization initiator

[0181] The example illustrates a procedure for attaching polymerization initiators to a substrate (in this case Si substrate).

[0182] Silicon wafer (Si) substrates, pre-cleaned as described in Example 1, were used for surface initiator-modification with CPTMS polymerization initiators using a chemical vapor deposition method: The substrates were placed in a rack and placed in a vacuum oven with 16 vials of 100 pL CPTMS (polymerization initiator liquid) at approximately 100°C for 30 minutes. The gauge pressure was lowered to -0.99 bar, whereby the CPTMS evaporated, and the substrates were left for 30 minutes in the vapor. Thereafter, the substrates were removed and left at ambient

[0183] IPTS / 200142442.1 temperature and ambient pressure for 24 h to anneal the silane (CPTMS) polymerization initiator layer.

[0184] Ellipsometry measurements before and after the polymerization initiator deposition did not show significantly different surface layer thickness, indicating the formation of a thin layer CPTMS polymerization initiator layer. Thus, the layer thickness from the CPTMS initiator molecule is not expected to contribute in a significant way to the surface polymer average dry film thickness in subsequent surface polymer formations.

[0185] Example 3

[0186] General method for assessing the rate of surface polymer formation

[0187] This example illustrates a general procedure for assessing the rate at which surface polymers are formed on a substrate with time. This procedure described in this Example was used in subsequent Examples.

[0188] Silicon wafer substrates were pre-cleaned as described in Example 1 , and CPTMS polymerization initiator-modified as described in Example 2. All substrates were then immersed at the same time in reaction composition comprising components for the surface polymerization (specified in the following Examples). Substrates were individually recovered from the reaction composition according to the following procedure: at minute 0, defined as 5 minutes after addition of (a solution of) catalyst activator (NaAsc), all substrates were immersed into the reaction composition. At certain “timestamps”, typically at 2, 5, 7.5, 10, 20, and 40 minutes following minute 0, unless specified otherwise, one substrate was withdrawn from the reaction composition, immediately subjected to a rinsing and drying processes, comprising sonication in Dl-water for 5 minutes, followed by sonication in acetone for 5 minutes, and air drying in ambient conditions (temperature, pressure) for at least a few minutes. Withdrawal of substrates at different timestamps allows assessment of surface polymer formation (propagation) as a function of time.

[0189] Following post-polymerization cleaning and drying, the average dry film thicknesses ( / ?) of the formed (collapsed) surface polymers were determined by ellipsometry. For each substrate, the average dry film thicknesses (in nm) were plotted against time (in minutes) at which the substrate was recovered. It is to be understood that the average dry film thickness (h) is directly proportional to the molecular weight by number average (Mn) as a result of the following equation:

[0190] IPTS / 200142442.1 where, n is the grafting density of the polymer chains, NA is Avogadro’s number and p is the bulk density of the polymer.

[0191] In visualizing ellipsometry data this way, the rate of surface polymer formation can be evaluated as a function of time. From here, the “rate” of a given reaction composition is referred to as the average dry film thickness of surface polymers which were obtained as a function of time.

[0192] Example 4

[0193] General method for assessing the lifetime (re-useability) of a reaction composition

[0194] The lifetime, i.e. the time where the reaction composition is re-useable for surface polymer formation), were assessed in the following manner: Silicon wafer substrates were pre-cleaned as described in Example 1, and polymerization initiator-modified as described in Example 2. Racks holding the substrates were exposed to a reaction composition to form surface polymers from the polymerization initiator sites (components of the reaction composition are indicated in the subsequent Examples). At minute 0, defined as 5 minutes after the addition of (a solution of) catalyst activator (NaAsc), a first substrate was immersed into the reaction composition for 10 minutes. At minute 10, the first substrate was removed / withdrawn from the reaction composition, rinsed and dried as described in Example 3, and another substrate was immersed in the reaction composition for 10 minutes, without changing the reaction composition or adding additional components. This was repeated until a total number of 12 substrates (unless otherwise indicated in the specific Examples) were subjected to surface formation for 10 minutes each, over the course of 120 minutes (unless otherwise indicated in the specific Examples).

[0195] After cleaning and drying the substrates with surface polymers, the average dry film thicknesses of the formed surface polymers were determined by ellipsometry. For each substrate, the average dry film thicknesses during a surface polymerization time of 10 minutes were plotted against the time (in minutes), where the substrate was withdrawn from the reaction composition, relative to the time of immersing the first substrate into the polymerization composition. In this way, the surface polymer- forming ability of the reaction composition was evaluated in 10-minute intervals throughout the 120 minutes selected as “cutoff’. The lifetime of a given reaction composition is defined as the duration of time where surface polymers may be formed with stable kinetics (rate), that is, where the average dry film thickness of surface polymers grown in 10-minute intervals are

[0196] IPTS / 200142442.1 consistently within + / -20%, or less, of the average dry film thicknesses measured in care of the immediately preceding substrate. Depending on the kinetic profile of the polymerization, it may take some time before surface polymers form with an average dry film thickness within + / -20%, or less.

[0197] Example 5

[0198] Monomer screening for surface polymer (polymer brush) formation using catalyst based on iron (Feb

[0199] In this example the inventors test the capabilities of the Fe mediated surface polymer forming technique on three different monomers: MM A, GM A and HEM A with three different polymerization activities.

[0200] The surface polymer forming liquid was prepared as follows:

[0201] To a 500 mL measuring cylinder, 32 mL of Fe catalyst solution (made from 2.6 g TPMA, 0.7 g FeCh- 6H2O, 250 mL Dl-water, and 250 mL EtOH) was mixed with 145 mL IM carbonate buffer and diluted with Dl-water to total volume of 500 mL. The mixture was transferred to a glass container (Container A), and 410 mL EtOH and 75 mL monomer (specified in Table 1) was added.

[0202] In a separate container (Container B), a solution of NaAsc (amounts specified in Table 1 in 15 mL Dl-water) was prepared. The content of Container B was poured into Container A, and the reaction composition was left for 5 minutes to activate the reaction composition for surface polymer formation. The content of Container A was poured into a reaction container.

[0203] Table 1. Specific amount of NaAsc used for each of the monomers.

[0204] 6 CPTMS-initiator-modified substrates (substrate Si, polymerization initiator CPTMS, precleaned as described in Example 1 and subjected to initiator-modification as described in Example 2) were placed in the reaction container (in a rack), and one substrate was withdrawn at a certain time to conduct a rate experiment as described in Example 3. Below, the average dry film thicknesses obtained at each time are reported in Table 2 and shown in Fig. 4.

[0205] IPTS / 200142442.1 Table 2. Average dry film thickness of substrates subjected to surface polymer formation for 2, 5, 7.5, 10, 20, and 40 minutes, respectively.

[0206] Fig 4 is a plot of surface polymer average dry film thickness as a function of reaction time for different monomers (a graphical representation of the results in Table 2). The MMA monomer polymerizes with a rate displaying a linear trend in the initial 10 minutes of surface polymerization. After 10 minutes, the rate of surface polymer formation may starts to decrease, and the rate of surface polymer formation seems to decrease further during the total time interval of 40 minutes. The GMA monomer polymerizes with a linearly trend during the surface polymer formation interval of 40 minutes, ending up with an average dry film thickness of PGMA similar to that of PMMA after 40 minutes. Polymerization of HEMA is slow compared to GMA and MMA however develops linearly during the 40 minutes surface polymerization interval.

[0207] In all cases, the Fe / TPMA catalyst / ligand complex were able to catalyze formation of surface polymers from initiator-modified sites on substrates. As expected, different kinetic profiles (initial rate of surface polymer formations) are obtained using different monomers for the Fe-catalyzed formation of surface polymers, with MMA monomer presenting the highest rate throughout the experiment, yet all monomers proved to be polymerizable using a Fe-catalyzed surface polymerization. This is reflected in Fig. 4, which is a graphical representation of the results in Table 2. The GMA polymerization showed a rate profile with a lower surface polymerization rate though more linear, as compared to MMA, however, during the 40 minutes surface polymerization interval, the final average dry film thicknesses of PMMA and PGMA were comparable. It is well known that the HEMA monomer generally has a low reactivity as compared to MMA and GMA under comparable polymerization conditions, and accordingly, surface polymers (PHEMA)

[0208] IPTS / 200142442.1 having lower average dry film thickness (in comparison with PMMA and PGMA) were expected and observed.

[0209] Example 6

[0210] Surface polymer formation with and without carbonate buffer

[0211] In this example the inventors seek to illustrate the effect of buffer in the Fe-catalyzed surface polymer formation. It is well known that some ionic Fe-species are pH dependent and precipitate as Fe-hydroxide species. Therefore the inventors wish to investigate the need for pH stabilization in form of a buffer Procedure and results of a polymer formation using MMA monomer is replicated herein from Example 5.

[0212] A surface polymer formation rate experiment was performed as described in Example 3 in a reaction composition with or without buffer. The results obtained are reported in Table 3.

[0213] The reaction compositions were prepared as follows:

[0214] Without buffer: To a Container Cl, 46.4 mg FeCL-6H2O, 164.8 mg TPMA, 16 mL DI- water and 16 mL EtOH were mixed and sonicated for 5 minutes. To a 500 mL measuring cylinder, the content of Container Cl was added and diluted to total volume of 500 mL using DI- water. The aqueous phase was transferred to a glass container (Container Al). 410 mL EtOH and 75 mL MMA monomer were added to Container AL In separate containers (Container Bl), a solution of NaAsc (4001 mg in 15 mL DI- water) was prepared. The content of Container Bl was poured into Container Al and the reaction composition was left for 5 minutes to activate the catalyst / ligand complex (Fe / TPMA).

[0215] The content of Container Al was poured into a reaction container.

[0216] With buffer: To a 500 mL measuring cylinder, 32 mL of Fe-catalyst solution (made from 2.6 g TPMA, 0.7 g FeCL-OHzO, 250 mL Dl-water, and 250 mL EtOH) was mixed with 145 mL IM carbonate buffer and diluted with Dl-water to total volume of 500 mL. The solution was transferred to a glass container (Container A2). 410 mL EtOH and 75 mL MMA monomer were added to Container A2. In separate containers (Container B2), a solution of NaAsc (4008 mg in 15 mL Dl- water) was prepared. The content of Container B2 was poured into Container A2, and the reaction

[0217] IPTS / 200142442.1 composition was left for 5 minutes to activate the catalyst / ligand complex (Fe / TPMA). The content of Container A2 was poured into a reaction container.

[0218] 6 CPTMS-initiator-modified substrates (substrate Si, initiator CPTMS), pre-cleaned as described in Example 1 and subjected to initiator-modification as described in Example 2 were placed in each of the reaction containers (with and without buffer, respectively), and one substrate was withdrawn at a certain time to conduct a rate experiment as described in Example 3 (time 0 = 5 minutes after activation of Fe / TPMA complex). Below, the measured average dry film thicknesses of surface polymers, obtained at each time of withdrawal from the reaction composition, are reported below in Table 3.

[0219] Table 3. Average dry film thicknesses for Fe-catalyzed surface polymer formation with and without buffered reaction composition.

[0220] Fig. 5 shows a plot of surface polymer average dry film thickness as a function of polymerization time with or without the use of buffer in the reaction composition. As observed, different rate profile was observed: with the use of buffer a fast linear trend was initially observed, however showing signs of slower polymerization rate after 10 minutes.

[0221] As evident from Table 3, surface polymers were formed using the Fe-catalyzed reaction composition. Interestingly, no buffer present seemed, at least with the MMA monomer, to lower the rate at which surface polymers were formed as compared to the rate of surface polymer formation using a buffer as part of the reaction composition. The difference in average dry film thicknesses between surface polymers formed using buffer and formed without buffer decreased at 40 minutes compared to the difference at 20 minutes (see Fig. 5). Importantly, the inventors

[0222] IPTS / 200142442.1 show that Fe catalyzed surface polymerization may be facilitated without the use of pH stabilization yet with an altered rate profile. The inventors hypothesize that pH stabilization may contribute to control surface polymerization to obtain surface polymers of a certain average dry film thickness in Fe-catalyzed surface polymer formations.

[0223] Example 7

[0224] Lifetime study of reaction compositions with Fe as catalyst

[0225] In this Example, the inventors illustrate the industrial potential of Fe-catalyzed surface polymerizations showing that a single reaction composition may be used for several surface polymer formation events during a prolonged period of time. Considering the ambient conditions (exposure to atmospheric oxygen) in aqueous medium, the Fe catalyst might precipitate as insoluble, catalytically inactive iron-oxides, especially with time.

[0226] The reaction composition was prepared as follows: To a Container C, 44.8 mg FeCL-bFLO, 166.0 mg TPMA, 16 mL Dl-water and 16 mL EtOH were mixed and sonicated for 5 minutes. To a 500 mL measuring cylinder, the content of Container C was added, and the total volume was adjusted to 500 mL adding Dl-water. The content of Container C was transferred to a glass container (Container A) with 410 mL EtOH and 75 mL MMA. In a separate container (Container B), a solution of NaAsc (4007 mg in 15 mL Dl-water) was prepared. The content of Container B was poured into Container A, and the reaction composition was left for 5 minutes to activate the Fe / TPMA complex for surface polymer formation. The content of Container A was poured into a reaction container.

[0227] 12 CPTMS-initiator-modified substrates (substrate Si, initiator CPTMS, pre-cleaned as described in Example 1, initiator- modification as described in Example 2) were subjected to a lifetime experiment as described in Example 4. Below in Table 4, the average dry film thicknesses of surface polymers obtained on each substrate are reported. The results were further plotted in Fig. 6 with the x-axis being time of withdrawal of a substrate, and the y-axis being the measured average dry film thickness on the substrate.

[0228] Table 4. Average dry film thicknesses obtained for 12 separate surface polymer formation events, each surface polymer formation being 10 minutes.

[0229] IPTS / 200142442.1

[0230] From Fig. 6, it was concluded that the average dry film thickness of the surface polymers seemed to be varying until a lifetime of approximately 40 minutes. Thereafter, the average dry film thickness of formed surface polymers seemed to be of comparable thicknesses, having regard to the standard deviation.

[0231] Surprisingly, surface polymer formation was catalyzed by Fe complexed with TPMA ligand during the whole investigated lifetime study (120 minutes, 10 minutes polymerizations), as can be seen from Table 4 and Fig. 6. As no discernible decrease in yielded average dry film thickness is observed, the inventors conclude that no Fe catalyst was “lost” in this study due to precipitation.

[0232] It is noted that after the “initial” approximately 30 minutes (substrate withdrawal at minute 10, 20, and 30 minutes, respectively), surface polymers are formed with a high degree of conformity throughout the tested 120 minutes lifetime study. The inventors suggest that a longer activation period following NaAsc addition may be needed to fully activate and stabilize the Fe / TPMA complex of the reaction composition. It could further be concluded that the Fe-catalyst-mediated surface polymer formation is useful for high volume manufacturing, as the lifetime of the reaction composition is at least 120 minutes.

[0233] IPTS / 200142442.1 After the 120 minutes lifetime study, the reaction container with the polymerization composition was kept closed until the following day (24 hours). After 24 hours, 6 CPTMS-initiator-modified substrates (substrate Si, initiator CPTMS, pre-cleaned as described in Example 1, initiatormodification as described in Example 2) were immersed into the reaction composition in the reaction container, and the 6 CPTMS-initiator-modified substrates were subjected to a rate study as described in Example 3. No additional components were added to the reaction composition prior to surface polymer formation (reaction composition was used as was following 24 hours storage). The results obtained are shown in Table 5 and graphically in Fig. 7.

[0234] Table 5. Fe-catalyzed surface polymer formation 24 hours after the experiments shown in Table 4 and Fig. 6 using the same (unaltered) polymerization composition.

[0235] Fig. 7 is a plot of surface polymer average dry film thickness (y-axis) as a function of polymerization time (x-axis). From Fig. 7, it was concluded that during the first 20 minutes of polymerization, the rate of surface polymerization proceeds linearly, and starts to converge, between minute 20 and 40, towards a constant average dry film thickness.

[0236] The Fe catalyst was surprisingly active even after 24 hours and able to catalyze the formation of surface polymers, as can be seen from Table 5 and Fig. 7. Furthermore, the reaction composition was stored 24 hours in ambient conditions, and even so the reaction composition was fully viable for surface polymer formation inferring that no Fe catalyst was lost after 24 h (precipitated ironoxides are usually strongly colored, and, thus, if precipitation has occurred, a change of color of the reaction composition could have been observed). In the experiment referred to in Table 5, the average dry film thicknesses of the formed surface polymer were fully comparable with the average dry film thickness obtained in the series of 10 minute polymerizations shown in Table 4 and Fig. 6. It was noted that in the case of the surface polymerizations after 24 hours storage of

[0237] IPTS / 200142442.1 the polymerization composition, no activation period was done (as no NaAsc was added), and as evident from Fig. 7, the surface polymerization proceeded with a rate, resulting in surface polymers having an average dry film thickness of approximately 60 nm after 40 minutes polymerization. The inventors speculate this may be due to the polymerization solution already being fully stabilized, and, surprisingly, not being inactivated due to time and / or exposed to atmospheric air which notoriously is known to cause inactivation of many catalysts in surface polymerizations.

[0238] Example 8

[0239] Fe-catalyzed surface polymer formation using reaction compositions comprising different solvents

[0240] In this Example, Fe-catalyzed surface polymer formation using buffered alcohols as solvent was investigated. The inventors hypothesize that changing the polarity of the reaction composition may alter the reactivity of the reaction composition.

[0241] The reaction composition was prepared as follows: To a 500 mL measuring cylinder, 32 mL of a Fe catalyst solution (2.6 g TPMA, 0.7 g FeCL- bfLO, 250 mL Dl-water, and 250 mL EtOH) was mixed with 145 mL IM carbonate buffer and diluted to a total volume of 500 mL using DI- water. The solution was transferred to a glass container (Container A), and 410 mL of alcohol (see Table 6) and 75 mL MM A monomer was added to Container A. In total, 3 Container A solutions were prepared. In a separate container (Container B), a solution of NaAsc (amounts specified in Table 6 plus 15 mL DI- water) was prepared. In total, 3 Container B solutions were prepared. The content of a Container B was poured into a Container A, and the reaction composition was left for 5 minutes to activate the Fe / TPMA complex for surface polymer formation. The content of Container A was then poured into a reaction container.

[0242] 6 CPTMS-initiator-modified substrates (substrate Si, initiator CPTMS, pre-cleaned as described in Example 1, subjected to initiator-modification as described in Example 2) were placed in each of the 3 reaction containers, and one substrate was withdrawn from each of the reaction containers at a certain time to conduct a rate experiment as described in Example 3. Below in Table 7 and in Fig 8, the average dry film thicknesses obtained at each time are reported.

[0243] Table 6. Amount of catalyst activator used with the solvents EtOH, MeOH, and iPrOH, respectively.

[0244] IPTS / 200142442.1

[0245] Table 7. Average dry film thicknesses of surface polymers formed in Fe-catalyzed surface polymer formation events using different carbonate-buffered solvents.

[0246] Fig. 8 is a plot of surface polymer average dry film thickness (y-axis) as a function of polymerization time (x-axis) (data reported in Table 7). For polymerizations using EtOH and iPrOH, respectively, a linear rate of surface polymerization was observed during the initial 20 minutes of surface polymer formation. Between 20 and 40 minutes, the linear rate of formation seemed to level off and converge towards a more constant rate of formation. Using MeOH in the reaction composition seemed to result in a more linear rate profile within the 40 minutes polymerization time interval. The longer the time with a linear rate of surface polymer formation, the higher the final average dry film thickness of the surface polymer. Thus, the final thickness of surface polymers (using MeOH as co-solvent) was about 70% higher than the average dry film thickness obtained with either EtOH and iPrOH for similar polymerization times.

[0247] Surprisingly, the Fe catalyzed surface polymerization could be carried out in various solvent systems with minor effect on polymerization rate (e.g., iPrOH versus EtOH), providing flexibility in choice of components. Other alcohols as solvent (MeOH versus EtOH) influence the polymerization rate, thus providing an increased kinetic control of the surface polymerization. In both instances, the Fe catalyst has proven applicable in different surface polymer manufacturing setups.

[0248] IPTS / 200142442.1 Example 9

[0249] Fe-catalyzed surface polymer formation in MeOH with and without buffer

[0250] In this example, the effect of buffer in the high performing MeOH based Fe-catalyzed surface polymerization was investigated.

[0251] For experiments with buffer, the reaction composition was prepared as follows: To a 500 mL measuring cylinder, 32 mL of Fe catalyst solution (2.6 g TPMA, 0.7 g FeCL-blFC), 250 mL DL water, and 250 mL EtOH) was mixed with 145 mL IM carbonate buffer and diluted to a total volume of 500 mL using DLwater. The solution was transferred to a glass container (Container A), and 410 mL of MeOH and 75 mL MMA monomer were added to Container A. In a separate container (Container B), a solution of NaAsc (4007 mg in 15 mL Dl-water) was prepared. The content of Container B was poured into Container A, and the reaction composition was left for 5 minutes to activate the Fe / TPMA complex for surface polymer formation. The content of Container A was poured into a reaction container.

[0252] For experiments without buffer, the reaction composition was prepared as follows: To a Container C, 46.2 mg FeCL- 6H2O, 167.2 mg TPMA, 16 mL Dl-water and 16 mL EtOH were mixed and sonicated for 5 minutes. To a 500 mL measuring cylinder, the content of Container C was added and diluted with DLwater to a total volume of 500 mL. The solution was transferred to a glass container (Container A), and 410 mL MeOH and 75 mL MMA were added. In a separate container (Container B), a solution of NaAsc (4007 mg in 15 mL DLwater) was prepared. The content of Container B was poured into Container A, and the reaction composition was left for 5 minutes to activate the Fe / TPMA complex for surface polymer formation. The content of Container A was poured into a reaction container.

[0253] 6 CPTMS-initiator-modified substrates (substrate Si, initiator CPTMS, pre-cleaned as described in Example 1, and initiator- modified as described in Example 2) were placed in each of the 2 reaction containers (holding the reaction composition with buffer and without buffer), and one substrate was withdrawn from each container at a certain time to conduct a rate experiment as described in Example 3. Below in Table 8, the average dry film thicknesses obtained at each time are reported.

[0254] IPTS / 200142442.1 Table 8. Average dry film thicknesses for Fe-catalyzed surface polymerization with and without buffer.

[0255] Fig. 9 shows the plot of surface polymer average dry film thickness (y-axis) as a function of polymerization time (x-axis). Using a buffer in the reaction composition appeared to lead to a linear rate of surface polymer formation throughout the experiment (40 minutes). Without a buffer, an activation period of 10 minutes (in addition to the 5 minutes after activation) appeared to apply, whereafter the polymerization kinetics appeared linear, resulting in an average dry film thickness similar to that obtained when using a buffer.

[0256] As can be seen from Table 8 and Fig. 9, the Fe catalyst was able to catalyze surface polymers. The inventors hypothesize that the presence of a buffer to some extent influence the rate of surface polymer formation, thus providing a linear trend as observed in Fig. 9. Without buffer, surface polymers were still formed with a linear rate profile, however, after an initial (believed to be) activation period of 10 minutes. Again, the inventors underline the importance of pH-stabilization features which seem to be beneficial for the Fe-catalyzed surface polymerization.

[0257] Example 10

[0258] Surface block copolymers of PMMA and PHEMA using Fe-catalyzed surface polymerizations In this example, the formation of surface block copolymers using Fe-catalyzed surface polymerization is shown. In this experiment, substrates were firstly subjected to surface polymer formation with MMA monomer according to the procedure described in Example 6 (without buffer), and then to a 40 minute HEMA surface polymerization as described in Example 5. In Example 6 (without buffer), the Fe-catalyzed surface polymerization displayed a linear rate of surface polymer formation between polymerization times of 10 and 40 minutes. A linear rate of

[0259] IPTS / 200142442.1 formation means that the surface polymerization is “living”, i.e., resulting in viable chain-ends which may be subjected to further surface polymerization.

[0260] For the PMMA layer, the surface polymer forming liquid was prepared as follows:

[0261] The reaction composition used in the first polymerization was prepared as follows: To a Container Cl, 45.7 mg FeCl3-H2O, 165.3 mg TPMA, 16 mL Dl-water and 16 mL EtOH (50:50 vol% water: EtOH) were mixed and sonicated for 5 minutes. To a 500 mL measuring cylinder, the content of Container Cl was added, and the total volume was adjusted to 500 mL adding Dl-water. The content of Container Cl was transferred to a glass container (Container Al) with 410 mL EtOH and 75 mL MMA. In a separate container (Container Bl), a solution of NaAsc (4009 mg in 15 mL Dl-water) was prepared. The content of Container B l was poured into Container Al, and the reaction composition was left for 5 minutes to activate the reaction composition for surface polymer formation. The content of Container Al was poured into a reaction container.

[0262] 6 CPTMS-initiator-modified substrates (substrate Si, initiator CPTMS, pre-cleaned as described in Example 1, and initiator- modified as described in Example 2) were placed in the reaction container, and one substrate was withdrawn at a certain time to conduct a rate experiment as described in Example 3. Below in Table 9 and Fig. 10, the average dry film thicknesses obtained at each time are reported.

[0263] For the PHEMA layer, the surface polymer forming liquid was prepared as follows:

[0264] The reaction composition used in the second polymerization was prepared as follows: To a Container C2, 45.7 mg FeCh-HtO, 166.0 mg TPMA, 16 mL Dl-water and 16 mL EtOH (50:50 vol% water:EtOH) were mixed and sonicated for 5 minutes. To a 500 mL measuring cylinder, the content of Container C2 and 145 mL of 1 M carbonated buffer was added, and the total volume was adjusted to 500 mL adding Dl-water. The content of Container C2 was transferred to a glass container (Container A2). 410 mL EtOH and 75 mL HEMA were added to Container A2. In a separate container (Container B2), a solution of NaAsc (4006 mg in 15 mL Dl-water) was prepared. The content of Container B2 was poured into Container A2, and the reaction composition was left for 5 minutes to activate the reaction composition for surface polymer formation.. The content of Container A2 was poured into a reaction container.

[0265] IPTS / 200142442.1 The 6 PMMA modified substrates and, as a reference, 1 CPTMS-initiator-modified substrate (substrate Si, initiator CPTMS, pre-cleaned as described in Example 1, and initiator-modified as described in Example 2) were placed in the reaction container and left for 40 minutes. Below in Table 9 and Fig. 10, the average dry film thicknesses obtained at each time are reported. The reference substrate (only PHEMA surface polymers) had surface polymer of PHEMA with an average dry film thickness of 9 ± 2 nm after 40 minutes polymerization.

[0266] Table 9. Average dry film thickness of PMMA and PMMA- PHEMA surface polymers.

[0267] The results were plotted as a bar plot showing the surface polymer average dry film thickness (y- axis) of PMMA formed at different polymerizations times (corresponding to a rate experiment) and PMMA-block-PHEMA (PMMA-b-PHEMA) after a 40 minute polymerization using HEMA monomer on the same PMMA substrates (x-axis). For all polymerization times, surface polymer propagation was catalyzed by the Fe catalyst.

[0268] Amazingly, in the range with a linear polymerization rate (10 and 20 minutes polymerization time during the PMMA formation), an average dry film thickness of 8 nm of PHEMA was added to the PMMA surface polymerized substrates, indicating near full availability for further surface polymer propagation of chain-ends. This underlines the livingness of the Fe-catalyzed surface polymerization, proving Fe a good candidate for controlled surface-initiated polymerizations under ambient conditions. At a polymerization time of 40 minutes, only 4 nm of PHEMA was added. This may be due to chain end terminations at longer PMMA polymerization times, leaving fewer active / viable ends that can be initiated in the subsequent PHEMA polymerization.

[0269] IPTS / 200142442.1 Surprisingly, for PMMA polymerization times of 2, 5 and 7.5 minutes only 3, 4 and 5 nm, respectively, PHEMA surface polymer was added. The inventors speculate that this may be attributed to a lower number of active chains formed during the induction period, leaving fewer initiating sites available for addition of PHEMA, see Table 9.

[0270] Example 11

[0271] Fe-catalyzed surface polymer formation with tBA monomer

[0272] In this example the inventors investigate the monomer, tBA, in an un-buffered Fe-catalyzed surface polymerization.

[0273] The reaction composition was prepared as follows: To Container C, 43.7 mg FeCL, 163.7 mg TPMA, 16 mL Dl-water and 16 mL EtOH (50:50 vol% water:EtOH) were mixed and sonicated for 5 minutes. To a 500 mL measuring cylinder, the content of Container C was added, and the total volume was adjusted to 500 mL adding Dl-water. The content of Container C was transferred to a glass container (Container A). 410 mL EtOH and 75 mL tBA were added to Container A. In a separate container (Container B), a solution of NaAsc (4001 mg in 15 mL Dl-water) was prepared. The content of Container B was poured into Container A, and the reaction composition was left for 5 minutes to activate the Fe / TPMA complex for surface polymerization. The content of Container A was poured into a reaction container.

[0274] 6 CPTMS-initiator-modified substrates (substrate Si, initiator CPTMS, pre-cleaned as described in Example 1, and initiator- modified as described in Example 2) were placed in the reaction container, and one substrate was withdrawn at a certain time to conduct a rate experiment as described in Example 3. Below in Table 10 and Fig. 11, the average dry film thicknesses obtained at each time are reported.

[0275] IPTS / 200142442.1 Table 10. Average dry film thickness of PtBA surface polymer.

[0276] Fig. 11 is a plot of surface polymer average dry film thickness (y-axis) as a function of polymerization time (x-axis). The rate of surface polymerization seemed to be linear during the polymerization time interval (40 minutes).

[0277] Incredibly, Fe is able to catalyze the formation of surface polymers, can be seen from Fig. 11 and Table 10. A slow increase in average dry film thickness is observed during the 40 minute polymerization time. The slow polymerization rate may offer excellent control over the final average dry film thickness of the formed surface polymer.

[0278] Example 12

[0279] Fe-catalyzed surface polymer formation with AMA monomer

[0280] In this example the inventors investigate the monomer, AMA, in an un-buffered Fe-catalyzed polymerization.

[0281] The reaction composition was prepared as follows: To a Container C, 44.5 mg FeCL, 163.9 mg TPMA, 16 mL DI- water and 16 mL EtOH (50:50 vol% water:EtOH) were mixed and sonicated for 5 minutes. To a 500 mL measuring cylinder, the content of Container C was added, and the total volume was adjusted to 500 mL adding DLwater. The content of Container C was transferred to a glass container (Container A). 410 mL EtOH and 75 mL AMA were added to Container A. In a separate container (Container B), a solution of NaAsc (4004 mg in 15 mL DLwater) was prepared. The content of Container B was poured into Container A, and the reaction composition was left for 5 minutes to activate the reaction composition for surface polymer formation. The content of Container A was poured into a reaction container.

[0282] IPTS / 200142442.1 6 CPTMS-initiator-modified substrates (substrate Si, initiator CPTMS, pre-cleaned as described in Example 1, and initiator- modified as described in Example 2) were placed in the reaction container, and one substrate was withdrawn at a certain time to conduct a rate experiment as described in Example 3. Below in Table 11 and Fig. 12, the average dry film thicknesses obtained at each time are reported.

[0283] Table 11. Average dry film thickness of PAMA surface polymer.

[0284] Fig. 12 is a plot of surface polymer average dry film thickness (y-axis) as a function of polymerization time (x-axis). As can be seen from Table 11 and Fig. 12, Fe is able to catalyze the formation of surface polymers with the AMA monomer. From Fig. 12, it may be concluded that the polymerization rate begins to decrease with polymerization times above approximately 25 minutes.

[0285] Example 13

[0286] Reference experiment: Test of effects of possible Cu impurities in Fe source

[0287] In this example the inventors investigate the possible contribution of potential copper impurities in the FeCE source on the polymerization kinetics illustrated in the examples above. Metal salts are generally known to possibly contain trace amounts of other metals, among these, copper (Cu). As copper is a well-known catalyst for surface-initiated controlled radical polymerizations, and as the Fe polymerizations in the Examples herein have shown remarkable results, the inventors investigate whether the possible Cu impurity may influence the surface polymerization.

[0288] The iron catalyst was prepared from FeCE-bFEO, and the expected Cu impurity was thus at maximum 0.002%, based on total impurity.

[0289] IPTS / 200142442.1 Calculation of the maximum amount of copper impurity in surface polymerizations performed in the above Examples: up to 168 mg of FeC , was used in the surface polymerizations. At maximum, 0.00336 mg can be expected to be copper (if copper impurity 0.002%). This equals 0.05 pmol Cu (molar mass of copper of 63.5 g / mol) yielding a concentration of 0.05 pmol / L in a 1 L reaction composition as in the Examples herein.

[0290] The reaction composition to test influence of copper impurities on surface polymerization was prepared as follows: TPMA (84.3 mg) was dissolved in 7 mL EtOH, and 9 mL CuCL solution was added (prepared by dissolving 1514 mg CuCh dihydrate in 1000 mL DL water). This Cu / TPMA solution was sonicated until all components were dissolved. In a 1000 mL flask 410 mL EtOH was added followed by 75 mL MM A monomer. In a measuring cylinder 160 pL of the prepared Cu / TPMA solution was diluted to 500 mL in DL water and added to the 1000 mL flask containing EtOH and MMA monomer. In a vial 4009.1 mg NaAsc was dissolved in 15 mL Dl-water. The NaAsc solution was added to the 1000 mL flask to activate the reaction composition. The reaction composition left to rest for 5 minutes. After mixing of all components the final copper concentration in the reaction composition was 0.08 pmol / L.

[0291] 4 CPTMS-initiator-modified substrates (substrate Si, initiator CPTMS, initiator-modified as described in Example 2) were placed in the reaction container holding the reaction composition. One substrate was withdrawn at a certain time to conduct a rate experiment (10, 20, 60, and 120 minutes). Below in Table 12, the average dry film thicknesses obtained at each time are shown.

[0292] Table 12 Average dry film thickness of PMMA surface polymer.

[0293] As expected, no significant surface polymerization could be achieved at a copper concentration of 0.08pmol / L. As the Cu concentration was 50% larger than what was expected from the possible copper impurities in Examples 4-12, the inventors conclude that any possible copper impurity originating from the Fe source could not influence the surface polymerizations.

[0294] IPTS / 200142442.1 Summarizing the results obtained in Examples 5-13

[0295] Amazingly, the inventors found that iron (Fe) used as catalyst in surface polymerizations provide an applicable alternative to conventional catalysts based on copper (Cu). Herein, it was shown that a Fe / TPMA catalyst / ligand complex was able to polymerize monomers having different polymerization activities. Surprisingly, Fe / TPMA may be applied in surface-initiated polymerization without the simultaneous use of a pH stabilization agent (e.g., a buffer), thus, indicating that the iron (Fe) may be quite uninfluenced by fluctuations in pH. However, pH stabilization or simply pH control during surface polymerization may provide additional positive effect on the control of the surface polymerization, at least in some surface polymerizations. This was, e.g., illustrated in the re-initiation experiment of Example 10 (preparation of PMMA-block- PHEMA surface polymer). In this Example, highly controlled propagation of viable chain-ends may be favoured by the presence of buffer.

[0296] The Fe catalyst was shown to be active for surface polymer formation for an extended period of time, see Example 7. Here, it was shown that the Fe catalyst was active for at least 24 hours.

[0297] The Fe catalyst was fully applicable in different solvent systems (e.g., MeOH, EtOH, and iPrOH), providing additional control of surface polymerization as well as surface polymerization rates (See Example 8).

[0298] The Fe catalyzed surface-initiated polymerization showed promising results in surface polymerization, making it a candidate for high-volume manufacturing. It is well-known the persons skilled in the art that using Cu mediated polymerizations, Cu residues may be undesired in many industries such as bio-medico and semiconductor industries. Thus, the inventors believe catalysts based on iron (Fe) offer a valuable alternative to the well-known Cu-based catalysts at the same time providing polymerization rate control. Furthermore, the Fe catalysts appear to be flexible and tolerant with regard to other components of the reaction composition (e.g., solvent, buffer), and, thus, may be a valuable tool for scale-up to high volume manufacturing where precise control of surface polymerization is needed.

[0299] IPTS / 200142442.1 List of reference numerals

[0300] 100 System

[0301] 102 Substrate

[0302] 103 Substrate displacement device 104 Reaction composition container

[0303] 105 Reaction composition

[0304] 106 Container

[0305] 107 Polymerization initiator chemistry

[0306] 109 Annealing oven 114 Cleaning container

[0307] 116 Cleaning agent / device

[0308] 118 Roll-to-roll processor

[0309] 120 Roller

[0310] 121 Sending roll 122 Receiving roll

[0311] 123 Flexible elongated substrate

[0312] IPTS / 200142442.1

Claims

1. Claims1. A method for forming surface polymers on a substrate comprising: providing a substrate having polymerization initiators on at least a portion of a surface of the substrate, exposing the substrate to a reaction composition comprising: a monomer, a catalyst / ligand complex formed from a Fe compound and a ligand, a catalyst activator, and a solvent, to form surface polymers via the polymerization initiators on the substrate.

2. A method according to claim 1 , wherein the Fe compound is a ferric compound or a ferrous compound.

3. A method according to claim 1 or 2, wherein the Fe compound is FeCh, FeB , FezCSCUh, FeCh, FeBr2, or FeSCb.

4. A method according to claim 1 or 2, wherein the Fe compound is FeCh.

5. A method according to claim 1, wherein the solvent is aqueous.

6. A method according to claim 5, wherein the solvent is a combination of methanol and water, ethanol and water, or isopropanol and water.

7. A method according to claim 1 , wherein the catalyst activator is selected from sodium ascorbate (NaAsc), ascorbic acid (Asc), hydrazine, hydrazine hydrate, sodium thiosulfate, sodium sulfite, sodium dithionite, glucose with GOX, and / or pyrogallic acid.

8. A method according to claim 1, wherein the reaction composition comprises a buffer, and / or a zwitterionic buffer.IPTS / 200142442.

19. A method according to claim 8, wherein the buffer is selected from carbonate buffer, glycine buffer, citrate buffer, phosphate buffer, acetate buffer, ammonium buffer (ammonium chloride / am- monia), formate buffer, and / or sodium ascorbate / ascorbic acid buffer.

10. A method according to claim 8, wherein the zwitterionic buffer is a Good’s buffer selected from MES, PIPES, MOPS, HEPES, CHES, CAPSO and / or CAPS.

11. A method according to claim 1 , wherein the ligand is a nitrogen-containing ligand.

12. A method according to claim 11, wherein the ligand is a heterocyclic nitrogen-containing ligand.

13. A method according to claim 11 or 12, wherein the ligand is selected from N,N,N’,N”,N’”- pentamethyldiethylene-triamine (PMDETA), tris[2-(dimethylamino)ethyl]amine (MeeTREN), tris(2-aminoethyl)amine (TREN), tris(2-pyridylmethyl)amine (TPMA), 1,1,4,7,10,10- hexamethyltriethylenetetramine (HMTETA), tetramethylethylenediamine (TMEDA), 1,4,8,11- tetramethyl-1,4,8,11-tetraazacyclotetradecane (Me4Cyclam), 2,2 ’-bipyridyl (BiPy), and / or pyridine.

14. A method according to claim 1, wherein the monomer is selected from methyl methacrylate (MMA), methacrylate (MA), allyl methacrylate (AMA), glycidyl methacrylate (GMA), hydroxyethyl methacrylate (HEMA), N-hydroxyethyl acrylamide (HEAM), 2-hydroxyethyl acrylate (HEA), tert-butyl acrylate (tBA), styrene, vinylimidazole (VI), N-vinylpyrrolidone, and vinylpyridine (VPY).

15. A method according to claim 1 , wherein the Fe compound is FeCh.

16. A method for forming a surface polymer on a substrate comprising: providing a substrate, exposing at least a portion of the surface of the substrate to a polymerization initiator, and exposing the substrate to a reaction composition comprising: a monomer, a catalyst / ligand complex formed from a Fe compound and a ligand,IPTS / 200142442.1a catalyst activator, and a solvent.

17. A method according to claim 16, wherein the Fe compound is a ferric compound or a ferrous compound.

18. A method according to claim 16 or 17, wherein the Fe compound is FeCh, FeBn, Fez SC , FeCF, FeBr2, or FeSCk19. A method according to claim 16, wherein the solvent is aqueous.

20. A method according to claim 19, wherein the solvent is a combination of methanol and water, ethanol and water, or isopropanol and water.

21. A method according to claim 16, wherein the catalyst activator is selected from sodium ascorbate (NaAsc), ascorbic acid (Asc), hydrazine, hydrazine hydrate, sodium thiosulfate, sodium sulfite, sodium dithionite, glucose with GOX, and / or pyrogallic acid.

22. A method according to claim 21, wherein the reaction composition comprises a buffer or a zwitterionic buffer.

23. A method according to claim 22, wherein the buffer is selected from carbonate buffer, glycine buffer, citrate buffer, phosphate buffer, acetate buffer, ammonium buffer (ammonium chloride / am- monia), formate buffer, and / or sodium ascorbate / ascorbic acid buffer.

24. A method according to claim 22, wherein the zwitterionic buffer is a Good’s buffer selected from MES, PIPES, MOPS, HEPES, CHES, CAPSO and / or CAPS.

25. A method according to claim 16, wherein the ligand is a nitrogen-containing ligand.

26. A method according to claim 25, wherein the ligand is a heterocyclic nitrogen-containing ligand.IPTS / 200142442.

127. A method according to claim 25 or 26, wherein the ligand is selected from N,N,N’,N”,N”’- pentamethyldiethylene- triamine (PMDETA), tris[2-(dimethylamino)ethyl]amine (MeeTREN), tris(2-aminoethyl)amine (TREN), tris(2-pyridylmethyl)amine (TPMA), 1,1,4,7,10,10- hexamethyltriethylenetetramine (HMTETA), tetramethylethylenediamine (TMEDA), 1,4,8,11- tetramethyl-l,4,8,ll-tetraazacyclotetradecane (Me4Cyclam), 2,2 ’-bipyridyl (BiPy), and / or pyridine.

28. A method according to claim 16, wherein the monomer is selected from methyl methacrylate (MMA), methacrylate (MA), allyl methacrylate (AMA), glycidyl methacrylate (GMA), hydroxyethyl methacrylate (HEMA), N-hydroxyethyl acrylamide (HEAM), 2-hydroxyethyl acrylate (HEA), tert-butyl acrylate (tBA), styrene, vinylimidazole (VI), N-vinylpyrrolidone, and vinylpyridine (VPY).

29. A method according to claim 16, wherein the Fe compound is FeCh.

30. A system for forming surface polymers on a substrate, the system comprising: a reaction composition container containing a reaction composition, said reaction composition comprising: a monomer, a catalyst / ligand complex formed from a Fe compound and a ligand, and a catalyst activator, and a substrate displacement device for bringing at least a portion of a polymerization initiator- modified substrate into contact with the reaction composition in the reaction composition container for a controlled time, wherein the controlled time is sufficient for surface polymers to be formed on the portion of the polymerization initiator-modified substrate.

31. A system of claim 30, wherein the substrate displacement device comprises any one of: a conveyor system, a programmable mechanical arm, or a roll-to-roll mechanism.IPTS / 200142442.

132. A system according to claim 30 or 31, further comprising a polymerization initiator container containing a polymerization initiator agent, wherein the substrate displacement device is configured to bring the at least a portion of the substrate for attachment of polymerization initiators into contact with the polymerization initiator agent to form polymerization initiators at the substrate surface, prior to bringing the at least a portion of the polymerization initiator-modified substrate into contact with the reaction composition.

33. A system according to claim 32, wherein the polymerization initiator container is a vacuum oven.

34. A system according to any one of claims 30 to 33 comprising one or more cleaning containers, the cleaning containers containing cleaning agents, wherein the substrate displacement device is configured to bring the at least a portion of the polymerization initiator-modified substrate into contact with the cleaning agents of the one or more cleaning containers prior to, or subsequent to, bringing the at least a portion of the polymerization initiator-modified substrate into contact with the reaction composition, and / or the substrate displacement device is configured to bring the at least a portion of substrate into contact with the cleaning agents in the one or more cleaning agents prior to, or subsequent to, bringing the at least a portion of the substrate into contact with the polymerization initiator.

35. A system according to any one of claims 30 to 34, further comprising a container for prewetting the at least a portion of the substrate prior to bringing the at least a portion of the substrate into contact with the reaction composition.

36. A system according to any one of claims 30 to 35, further comprising a reaction composition management system.

37. A system according to claim 36, wherein the reaction composition management system comprises one or more sensors in relation to the reaction composition container.

38. A system according to claim 37, wherein the sensors are configured to measure the pH of the reaction composition and / or the molecular oxygen concentration in the reaction composition.IPTS / 200142442.

139. A system according to any one of claims 30 to 38, further comprising one or more flow control devices.

40. A system according to claim 39, wherein the one or flow control devices are selected from circulation pumps, flow guidance grids, filters, and / or mechanical stirring means.

41. A system according to any one of claims 30 to 40, further comprising a heating device for annealing the substrate prior to, or subsequent to, bringing the at least a portion of the polymerization initiator-modified substrate into contact with the reaction composition.

42. A polymer formed on at least a portion of at least a surface of a substrate by a method according to any one of claims 1 to 29.IPTS / 200142442.1

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