Composition for forming polymer brush

Abstract

To provide novel chemical solutions suitable for forming polymer brushes on a surface of a solid part, methods of forming polymer brushes on the surface of a solid part using the chemical solutions as well as solid parts having polymer brushes coated onto the surface and methods of use therefor.SOLUTION: Reaction compositions used for forming polymer brushes on a surface of solid parts comprises: at least one polymerization composition; at least one activation agent; and one or more monomers provided as one or more of (i) part of the polymerization composition, (ii) part of the activation agent, or (iii) a discrete composition. The at least one polymerization composition comprises: a solvent; one or more dormant transition metal catalysts derived from Cu or Fe; and a ligand capable of coordinating with the transition metal, wherein the activation agent comprises one or more deoxidizing agents, and wherein the at least one polymerization composition and the at least one activation agent are separate compositions.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to novel chemical solutions (reaction compositions and polymerization compositions) suitable for forming polymer brushes on the surface of a solid part. The present invention further relates to a method for forming a polymer brush on the surface of a solid part using the novel composition, and to a solid part having a polymer brush coated on the surface. The use of such polymer brush-coated solid parts is also included.

Background Art

[0002] Well-defined polymer structures on solid parts are becoming increasingly important in many technologies. Such polymer structures are often referred to as polymer brushes. Basically, a polymer brush is an aggregate of polymers connected to a substrate at one end, and typically is a solid part made of, for example, metal, plastic, ceramic, and other solid materials. The emergence of new polymerization technologies has facilitated the specific design and synthesis of polymer brushes with precise molecular control and desired properties. Polymer brushes have been explored for the past 20 years, but they have previously had limited use as functional surface coatings showing long-term mechanical stability and chemical robustness. However, in recent years, polymer brushes have been found to have more applications than nanoscale "building blocks" with a wide range of uses from redox activity to biocompatibility and surface modification, and due to the flexibility of polymer brushes, highly tuned thin films of polymer brushes can be created with respect to component composition, thickness, graft density, and architecture.

[0003] In fact, polymer brushes are a powerful tool in the assembly of incompatible materials that cannot be easily combined by adhesion or other conventional interlocking methods. Polymer brushes provide bonding of materials, even if they are substantially invisible and transparent.

Summary of the Invention

Problems to be Solved by the Invention

[0004] The formation and attachment of polymer brushes to a solid surface are specialized operations that require specialized equipment. Furthermore, the chemical reaction (polymerization) is time-consuming and complex. Thus, most polymer brush-coated surfaces are prepared in specialized facilities. One of the main challenges is that the reaction mixture required for the formation of polymer brushes is unstable, so special reaction conditions such as a strict inert atmosphere and temperature control are required to control the formation and reaction of polymer brushes.

[0005] Therefore, there is a need to develop methods and reagents for the easier and less complex production of polymer brush-coated surfaces.

Means for Solving the Problems

[0006] In a first aspect, the present invention relates to a reaction composition. The reaction composition is used to form a polymer brush on the surface of a solid portion. The reaction composition includes at least one polymerization composition and at least one activator. In particular, the polymerization composition includes one or more dormant transition metal catalysts, and the activator includes one or more deoxidizers. The main advantage of the reaction composition according to the present invention is that the polymerization composition can be stabilized during storage, and further, the polymerization composition can be activated as required by the activator.

[0007] The reaction composition preferably includes at least one polymerization composition and at least one activator provided as separate compositions. Thereby, the polymerization composition can be activated as required.

[0008] In a second aspect, the present invention relates to a method for forming a polymer brush on a solid portion. This method includes providing a solid portion having a polymerization initiator immobilized on the surface of the solid portion, and further includes contacting the solid portion with a reaction composition formed by mixing a polymerization composition and an activator.

[0009] In one embodiment, the present invention relates to a method for forming a polymer brush on a solid part having a polymerization initiator immobilized on the surface of the solid part, the method comprising: providing a polymerization composition and an activator; mixing the polymerization composition and the activator to form a reaction composition; and contacting the reaction composition with the solid part, thereby initiating surface polymerization on the solid part, whereby a polymer brush is formed on the surface of the solid part via the polymerization initiator. The method includes the steps above.

[0010] The present invention further relates to a polymer brush-coated solid part obtainable by the method according to the present invention.

[0011] The present invention also contemplates the use of the reaction composition according to the present invention for forming a polymer brush on the surface of a solid part.

[0012] The present invention enables the use of polymer brush-coated solid parts for preparing various products for various purposes.

[0013] The polymerization composition also forms part of the present invention. The polymerization composition comprises one or more dormant transition metal catalysts. The polymerization composition has unique stability, thereby enabling storage over a period while maintaining reaction performance. The polymerization composition can be activated as required by the presence of one or more dormant transition metal catalysts.

[0014] Certain embodiments of the present invention are shown in the accompanying drawings. The drawings are not intended to limit the present invention in any way.

Brief Description of the Drawings

[0015]

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DETAILED DESCRIPTION OF THE INVENTION

[0016] The present invention and its aspects are described in more detail below.

[0017] The present invention relates to a reaction composition comprising at least one polymerization composition and at least one activator, wherein the at least one polymerization composition comprises one or more dormant transition metal catalysts, and the activator comprises one or more deoxidizers.

[0018] The overlapping composition contains at least one dormant transition metal catalyst. That is, the overlapping composition can contain one dormant transition metal catalyst, or one or more dormant transition metal catalysts. For example, the overlapping composition can contain 2, 3, 4, 5, or more dormant transition metal catalysts. In some embodiments, several overlapping compositions such as 2, 3, or 4 can be provided, and each or some of the overlapping compositions containing one or more transition metal catalysts can be provided.

[0019] The dormant transition metal catalyst is optionally derived from copper (Cu), iron (Fe), aluminum (Al), cadmium (Cd), tungsten (W), rhenium (Re), ruthenium (Ru), platinum (Pt), titanium (Ti), manganese (Mn), nickel (Ni), samarium (sm), or palladium (Pd). Combinations of such dormant transition metal catalysts are also included. Non-limiting examples of the dormant transition metal catalyst include the following, Cu: Cu2O, CuO, and Cu(O) Fe: FeO, Fe2O3, Fe3O4 Sm: Sm2O3 Al: Al2O3 Cd: CdO W: WO3 Re: ReO3, Re2O7 Ru: RuO2 Pt: PtO2 Ti: TiO2 Mn: MnO2 Ni: NiO Pd: PdO are included.

[0020] The dormant (dormant) metal can be provided in combination with a ligand that can coordinate with the transition metal in particular. Thereby, the catalytic effect is achieved. Thus, the transition metal related to the ligand forming the transition metal catalyst can be dormant or activated.

[0021] Usually, when the transition metal is oxidized, it becomes dormant (inactive).

[0022] In one embodiment, the one or more dormant transition metal catalysts are derived from copper (Cu). In particular, when the one or more dormant transition metal catalysts are derived from copper (Cu), the transition metal catalyst can be selected from among Cu2O, CuO, Cu(O), and CuSO4*5H2O. Combinations of such transition metal catalysts are also included.

[0023] In another embodiment, the one or more dormant transition metal catalysts are derived from iron (Fe). In particular, when the one or more dormant transition metal catalysts are derived from iron (Fe), the transition metal catalyst may be selected from among FeO, Fe2O3, and Fe3O4. Combinations of such transition metal catalysts are also included.

[0024] In a third embodiment, the dormant transition metal catalyst is derived by using both copper (Cu) and iron (Fe). Thus, the dormant transition metal catalyst can be a combination of Cu2O, CuO, Cu(O), and CuSO4*5H2O, and FeO, Fe2O3, and Fe3O4.

[0025] The dormant transition metal catalyst can initiate polymerization when activated.

[0026] In one embodiment of the reaction composition of the present invention, the one or more polymerization compositions and the one or more activators are provided as separate solutions, powders or particulate preparations. Providing the polymerization composition and the activator as separate or distinct solutions, powders, or particulate preparations ensures the beneficial stability of the polymerization composition because the dormant transition metal catalyst cannot be converted or regenerated to its active form without the presence of the activator.

[0027] The activator or agent contains one or more deoxidizers. The deoxidizer of the activator can activate the dormant transition metal catalyst of the polymerization composition by consuming oxygen from an aqueous solution. Thus, the removal of oxygen enables the dormant metal catalyst to be regenerated into an active metal catalyst. Some of the deoxidizer can also directly reduce the dormant metal catalyst to an active metal catalyst. As described above, the dormant metal catalyst is formed between the transition metal and the ligand.

[0028] In some embodiments, the oxygen scavenger of the activator is selected from sodium ascorbate (NaAsc), ascorbic acid, hydrazine hydrate, sodium hypophosphite, a mixture of iron powder and sodium chloride, bicarbonate, citric acid, and pyrogallic acid, and mixtures thereof. In certain aspects, the oxygen scavenger is selected from sodium ascorbate and / or ascorbic acid. In particular, the oxygen scavenger can be provided as a liquid, powder, or particulate preparation.

[0029] To drive the polymerization reaction, the reaction composition further comprises one or more monomers. The one or more monomers can be provided as part of the polymerization composition and / or as part of the activator. Additionally, the one or more monomers can be provided as a separate or distinct composition that is mixed with the polymerization composition and the activator, thereby forming the reaction composition. Non-limiting examples of monomers include acrylate, methacrylate, halogen-substituted alkenes, acrylamide, methacrylamide, and styrene, and mixtures thereof. The monomers can optionally have functional groups that assist in the disproportionation of the active transition metal catalyst. Non-limiting examples of functional groups include amide, sulfoxide, carbonate, and onium.

[0030] Specific acrylate monomers include, but are not limited to, methyl acrylate, ethyl acrylate, and lauryl acrylate. Specific methacrylic acid monomers include, but are not limited to, methyl methacrylate (MMA), 2-hydroxyethyl methacrylate (HEMA), glycidyl methacrylate (GMA), ethyl methacrylate, butyl methacrylate, and lauryl methacrylate. Specific halogen-substituted alkene monomers include, but are not limited to, vinyl chloride, vinylidene difluoride, tetrafluoroethylene, chlorotrifluoroethylene, and hexafluoropropylene. Specific acrylamide monomers include, but are not limited to, acrylamide, N-isopropylacrylamide, N-tert-butylacrylamide, and N-hydroxyethylacrylamide. Specific methacrylamide monomers include, but are not limited to, N-isopropylmethacrylamide, methacrylamide, N-tert-butyl methacrylate, and N-hydroxyethyl methacrylate. Specific styrene monomers include, but are not limited to, styrene, 4-methylstyrene, 2,3,4,5,6-pentafluorostyrene, p-divinylbenzene, and 4-chlorostyrene.

[0031] As described above, the reaction composition can further include one or more ligands that bind to the transition metal. The one or more ligands can be provided as part of the polymerization composition and / or as part of the activator. Further, the one or more ligands can be provided as a separate or distinct solution that is mixed with the polymerization composition and the activator, thereby forming the reaction composition. The ligand is preferably added in excess to ensure sufficient availability of the ligand for the transition metal. Specific ligands include, but are not limited to, nitrogen-containing ligands such as N,N,N’,N’’,N’’’-pentamethyldiethylenetriamine (PMDETA), tris[2-(dimethylamino)ethyl]amine (Me6TREN), tris(2-aminoethyl)amine (TREN), tris(2-pyridylmethyl)amine (TPMA), and 2,2’-bipyridyl (BiPy).

[0032] The reaction composition can further include one or more solvents. The one or more solvents can be provided as part of the polymerization composition and / or as part of the activator. Further, the one or more solvents can be provided as a separate solution or distinct solutions that are each mixed with the polymerization composition and the activator, thereby forming the reaction composition. Specific solvents include, but are not limited to, alcohols, polar aprotic solvents, methylene carbonate, ethylene carbonate, propylene carbonate, ethyl lactate alcohol, ionic liquids, and water, and mixtures thereof. Methyl alcohol (methanol) and ethyl alcohol (ethanol) can be suitable solvents for the polymerization composition as they can act as a dormant transition metal catalyst and optionally a suitable carrier for the monomer when the monomer is present in the polymerization composition. Water can be a suitable solvent for the activator. The concentration of each component or compound in the composition / drug is typically in the range of 0.1 nM to 35 M. Specific examples include, but are not limited to, 1 nM, 5 nM, 10 nM, 50 nM, 1 M, 5 M, 10 M, 20 M, and 30 M. It should be understood that the concentrations of each component or compound can be the same or different. In certain embodiments, the monomer concentration can be from 0.01 M to 5 M. In certain embodiments, the concentration of the deoxidizer can be from 0.010 to 0.045 M. In one embodiment, the concentration of the ligand is 0.046 M. In one aspect, the concentration of the solvent is from 0.1 to 35 M. In certain embodiments, the concentration of the catalyst is from 1.0 ppb to 500.0 ppm.

[0033] Accordingly, the reaction composition of the present invention is such that the dormant transition metal catalyst is activated by mixing the polymerization composition and the activator. As described above, the polymerization composition and / or the activator can optionally include additional compounds such as monomers, ligands, solvents, or mixtures thereof. These additional compounds can optionally be provided as separate compositions that are mixed with the polymerization composition and / or the activator.

[0034] The overlapping composition can be suitably prepared in several ways by adding a dormant transition metal catalyst to a suitable solvent. For example, (1) adding the transition metal catalyst as a nanoparticle powder and then oxidizing the powder mainly by the atmosphere to a dormant form, (2) preparing the transition metal catalyst in situ from the disproportionation of salts of the transition metal catalyst and then oxidizing it by the atmosphere to create mainly a dormant form, (3) adding the solid form of the transition metal catalyst to the solvent, spinning (stirring) the mixture to generate and liberate nanoparticles of the transition metal catalyst in the solvent, and then oxidizing the metal particles by the atmosphere, (4) passing it through a Cu tube or a Cu-packed bed reactor in a flowing state, etc. The preparation of the overlapping composition can preferably be carried out at room temperature.

[0035] The activator can be appropriately prepared by mixing various components and optionally stirring. The preparation of the activator can preferably be carried out at room temperature, although any temperature can be appropriate.

[0036] Once the overlapping composition and the activator are prepared, they can be stored until use. Since each is in a dormant state, i.e., no chemical reaction occurs, excellent storage stability for several months to several years is expected. The overlapping composition and the activator can be stored at any suitable temperature. In some embodiments, they can be stored at a reduced temperature, for example, below 5 °C or below 8 °C.

[0037] An important aspect of the present invention is a method of forming a polymer brush on a solid part, the method comprising providing a solid part having a polymerization initiator immobilized on the surface of the solid part, the method further comprising contacting the solid part with a reaction composition as defined herein, which is formed by mixing an overlapping composition and an activator.

[0038] In a particular embodiment of the method, the method comprises providing an overlapping composition as defined herein, providing an activator as defined herein, Mix the overlapping composition and the activator to form a reaction composition as defined herein, contact the reaction composition with the solid portion, thereby initiating surface polymerization, whereby a polymer brush is formed on the surface of the solid portion via a polymerization initiator.

[0039] In some embodiments of the method according to the invention, the presence of oxygen can be reduced to facilitate the formation of the polymer brush. The presence of oxygen can be appropriately reduced to 70% or more, such as, for example, 70%, 75%, 80%, 85%, 90% or 95%. However, the formation of the polymer brush can be carried out in an atmosphere having an oxygen concentration of 0 to 100%. In certain embodiments, the formation of the polymer brush is carried out under normal atmospheric conditions.

[0040] The solid portion can be suitably made from a material including a metal (e.g., aluminum, steel plate, titanium, nickel, gold, silver, platinum, chromium, copper, iron, and alloys of various metals), glass, carbon or graphite, ceramic, composite, or plastic, or an outer coating of such a material. The solid portion can be conductive or non-conductive.

[0041] The solid portion has a polymerization initiator immobilized on its surface. Thereby, the solid portion is activated (activated solid portion). Methods for binding such a polymerization initiator are well known in the art. Methods for immobilizing the polymerization initiator are described, for example, in International Publication No. WO 2014 / 075695 A1. Generally, the polymerization initiator is such that it can covalently bond to the surface of the solid portion.

[0042] The polymerization initiator can be made using a predefined surface chemistry to enable immobilization onto the surface of the solid part, depending on the material from which the solid part is made and on the properties of the polymer brush to be formed. Immobilization of the initiator usually involves binding organic molecules to the surface of the solid part by natural grafting or electrografting. Types of natural grafting include, but are not limited to, silane, phosphonic acid, and diazonium grafting. Types of electrografting include, but are not limited to, diazonium, iodonium, and sulfonium grafting. General grafting of such compounds can be seen in FIGS. 3A and 3B.

[0043] Binding of the polymerization initiator to the surface can be done in either a one-step or two-step manner. In the one-step method, grafting of a benzyl halide (mostly benzyl chloride) moiety onto the surface by diazonium grafting or silane grafting is used (see FIGS. 4 and 5 for the silane grafting version). The benzyl halide moiety acts as the polymerization initiator for the graft layer. The two-step method is a way of surface grafting an organic compound with a nucleophilic group in the first step and binding the initiator moiety using the nucleophilic group in the second step (see FIG. 6 for the hydroxy diazonium version). The nucleophilic agent can include, but is not limited to, a hydroxyl group or an amine group. In the second step, the nucleophilic agent is reacted with an electrophilic agent to add the initiator moiety and form a covalent bond between the two. Immobilization is further described below.

[0044] Silane grafting one-step: The initiator can be immobilized onto the surface in one step by silane grafting of a trialkoxysilane with a benzyl halide group (see FIG. 4).

[0045] Silane grafting is usually carried out by either of two methods: vapor deposition or solution grafting.

[0046] Diazonium grafting one-step: The initiator can be immobilized on the surface in one step by diazonium grafting of the diazonium salt with a benzyl halide group (see Figure 5).

[0047] Diazonium grafting is usually carried out by any of three methods: electrochemical, spontaneous, or chemical grafting.

[0048] Diazonium grafting in two steps: Another route for initiator immobilization is a two-step process (see Figure 6). The first step is the diazonium grafting of diazonium salts containing a nucleophilic group (OH). In the second step, a halogen-containing group is added by a nucleophilic acyl substitution reaction to obtain an immobilized polymerization initiator.

[0049] Other methods for immobilizing the initiator are well known in the art.

[0050] By the method of the present invention, a solid part having a polymerization initiator immobilized on its surface is contacted with a polymerization composition and an activator. The mixing of the polymerization composition and the activator results in the formation of a reaction composition, which enables the formation of a polymer brush via the polymerization initiator on the surface of the solid part upon contact with the solid part on which the polymerization initiator is immobilized (i.e., the activated solid part). It should be understood that other components or solutions can also be mixed with the polymerization composition and the activator, such as monomers, ligands, etc., as described above. These additional components or compounds may be part of the polymerization composition or the activator, or may be provided as separate solutions or components. Furthermore, it should be understood that the polymerization composition, the activator, and optionally other solutions or components may be mixed before contacting the solid part, or may be mixed upon contact with the solid part.

[0051] Suitable polymerization compositions, activators, and any other solutions or components are those specified above.

[0052] In one embodiment of the method of the present invention, the solid portion on which the polymerization initiator is immobilized is immersed in the reaction composition. The formation of the polymer brush can be carried out under ambient conditions (temperature, atmosphere).

[0053] In another embodiment of the method of the present invention, the reaction composition is sprayed or coated onto the solid portion. The reaction composition can be further brought into contact with the solid portion by applying a liquid film to the surface of the solid portion on which the polymerization initiator is fixed, for example, by applying so-called spin coating and drop coating techniques and the like.

[0054] In certain embodiments, the solid portion is selected from metals or alloys, glass, ceramics, plastics, carbon-based materials, and composite materials, or combinations thereof. Non-limiting examples are stainless steel, glassy carbon, and thermoplastic resins.

[0055] In some aspects, the reaction composition can be cooled or heated before or during contact with the solid portion. Suitable temperatures are -20°C to 120°C, such as room temperature (about 20°C) to 120°C. Specific temperatures include, but are not limited to, -20°C, 0°C, room temperature (about 20°C), 30°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C.

[0056] The solid portion having the polymerization initiator immobilized thereon and the reaction composition are typically kept in contact with each other for a suitable period, such as 0.1 seconds to 5 hours. Suitable times include, but are not limited to, 1 second, 2 seconds, 30 seconds, 1 minute, 5 minutes, 30 minutes, 1 hour, 2 hours, 3 hours, 4 hours, and 5 hours.

[0057] In some applications, the method of the present invention may be repeated to form another layer of polymer brush on top of an existing one. Thereby, so-called block polymers can be formed on a solid part. It should be understood that the repeated method can include a polymer different from that used when forming the first layer of the polymer brush. The method of the present invention can be repeated multiple times to prepare more complex properties of the polymer brush. For preparing block polymers, halogen atoms on the previously formed polymer brush can be suitably used for further formation of the polymer brush.

[0058] Furthermore, the present invention relates to a polymer brush-coated solid part obtainable by the method described herein. Such solid parts having a polymer brush-coated surface prepared by the method according to the present invention find many applications. Non-limiting examples are for adhesion, corrosion resistance, providing an antibacterial or low-friction surface, and preparing a decorative design.

[0059] The principle of the method of the present invention is shown in Figure 2. As can be seen from the figure, a solid part (activated solid part) with a polymerization initiator fixed thereon is provided. Such an activated solid part is brought into contact with a reaction composition (obtained by mixing a polymerization composition and an activator). As shown, each of the polymerization composition and the activator (or both) can include one or more individual solutions. When mixed, a reaction composition is formed. When the reaction composition and the solid part are contacted (at an appropriate temperature for an appropriate time), a polymer brush is formed on the surface of the solid part.

[0060] Polymer brushes (polymer brush structures) can be used in a variety of applications including, but not limited to, the binding of polymer materials to metals for encapsulation purposes, the binding of functional thermoplastic plastics to glass for sensor applications, functional surfaces such as antibacterial surfaces, low friction surfaces on glass or superhydrophobic self-cleaning surfaces, and the efficient binding of polymer brush-coated composite fillers such as carbon fibers, graphene, particles, etc. to a polymer matrix, such as a thermoplastic material, for creating materials such as metals, plastics, etc.

[0061] Accordingly, according to the above, the present invention relates to the use of polymer brushes prepared according to the methods disclosed herein for the binding of polymer materials to metals, the binding of functional thermoplastic plastics to glass, the binding of polymer brush-functionalized composite fillers as composite materials to a polymer matrix, forming a functional surface on a glass, metal or plastic material, forming a low friction surface on a glass, metal or plastic material, and forming a self-cleaning surface on a glass, metal or plastic material.

[0062] The present invention is further illustrated by the following non-limiting examples. Examples

[0063] Example 1 Preparation of Polymer Brushes from 2-Hydroxyethyl Methacrylate (HEMA) Preparation of Polymerization Compositions 12 mL of water, 6 mL of methyl alcohol (MeOH), 12 mL of HEMA, and 0.2208 mL of N,N,N’,N’’,N’’-pentamethyldiethylenetriamine (PMDETA - ligand) were mixed in a flask, a Teflon® magnet wrapped with Cu wire was added to the flask, and the mixture was rotated in the flask at 400 rpm for 2 or 5 hours depending on the desired concentration of Cu spice. Two different arbitrary Cu concentrations were designated as "2 / 5" and "5 / 5". Thereafter, the Teflon magnet wrapped with Cu wire was removed and the solution was stored at 2 - 5 °C until use.

[0064] Polymerization in 5 / 5 Solution 5 mL of the 5 / 5 polymerization composition was purged with argon for 3 minutes. Next, 9 mg / mL of NaAsc (activator) was added to the polymerization composition to form a reaction composition together with the activated solid part (glassy carbon). The reaction composition was stirred with the activated solid part (glassy carbon) for 40 minutes.

[0065] After polymerization, the solid part coated with the polymer brush was taken out of the liquid and washed with acetone. By this treatment, a uniformly formed polymer brush with a thickness of 28.0 nm was obtained.

[0066] Polymerization in 2 / 5 Solution 5 mL of the 2 / 5 polymerization composition was purged with argon for 3 minutes. Next, 9 mg / mL of NaAsc (activator) was added to the polymerization composition to form a reaction composition together with the activated solid part (glassy carbon). The reaction composition was stirred with the activated solid part for 40 minutes.

[0067] After polymerization, the solid part coated with the polymer brush was taken out of the liquid and washed with acetone. By this treatment, a uniformly distributed polymer brush with a thickness of 33.6 nm was obtained.

[0068] Polymerization by Liquid Film on Surface 4 mL of the 5 / 5 polymerization composition was purged with argon for 3 minutes. Next, specific amounts (2 mg / mL, 5 mg / mL, and 9 mg / mL) of NaAsc (activator) as a powder were added to the polymerization composition to form a reaction composition. A thin film (0.02 mL / cm 2 ) of the reaction composition was placed on the surface of the activated solid part (glassy carbon), reacted for 10 minutes, and then washed with 1) deionized water, 2) acetone, and 3) pentane. The thin film of this reaction composition was added to the surface of the activated solid part, and the reaction and washing were repeated 3 times.

[0069] After polymerization, the liquid film was washed from the solid part coated with the polymer brush this time. A layer of polymer brush uniformly formed on the solid part was observed.

[0070] Spray Polymerization 6 mL of the 5 / 5 copolymer composition was purged with argon for 3 minutes. Next, the solution was transferred to a spray, and specific amounts of NaAsc (activator) (2 mg / mL, 5 mg / mL, and 9 mg / mL, respectively) were added to obtain a reaction composition in spray form. The activated solid part (glass-like carbon) was spray-coated with the reaction composition on the surface. After reacting the spray-coated surface for 10 minutes, it was washed off. The processes of spray coating, reaction, and washing were repeated 4 times.

[0071] After polymerization, the polymer brush-coated solid part was washed by sonication in 1) deionized water, 2) HPLC-acetone, and 3) pentane.

[0072] The polymer brush-coated solid part was inspected, and it was observed that a layer with uniformly distributed polymer brushes was formed on the solid part.

[0073] Polymerization Using Cu Nanoparticles (NP’s) as Catalyst 12 mL of water, 6 mL of methyl alcohol (MeOH), 12 mL of HEMA, 0.2208 mL of N,N,N’,N’’,N’’-pentamethyldiethylenetriamine (PMDETA - ligand), and 1 mg of Cu2O nanoparticles (NP) (with a diameter of less than 250 nm) (polymerization composition) were mixed in a flask. The solution was stored at 2 - 5 °C until use.

[0074] 5 mL of the above polymerization composition was purged with argon and treated for 3 minutes. Now, 9 mg / mL of NaAsc (activator) was added as a powder, and a reaction composition was formed together with the activated solid part (glass-like carbon). The reaction composition was stirred with the activated solid part for 40 minutes.

[0075] After polymerization, the polymer brush-coated solid part was washed by sonication in 1) deionized water, 2) HPLC-acetone, and 3) pentane.

[0076] Example 2 Preparation of Polymer Brushes from Glycidyl Methacrylate (GMA) Monomer Preparation of Polymerization Compositions with Different Cu Concentrations In a solution of 5 mL of DI-water and 0.050 mL of PMDETA, a Teflon magnet wrapped with a Cu wire was stirred for 30 minutes. Subsequently, the Cu wire-wrapped Teflon magnet was flushed with HPLC-acetone and transferred to another glass container.

[0077] Here, 32.46 ml of MeOH, 32.46 ml of DI-water, and 0.729 ml of N,N,N’,N’’,N’’-pentamethyldiethylenetriamine (PMDETA-ligand) were added to a second glass container with the prepared Cu wire-wrapped Teflon magnet. The Cu wire-wrapped magnet was stirred in the solution at 400 rpm for a sufficient time to obtain a Cu catalyst spice with the desired concentration. Subsequently, the Teflon magnet wrapped with a Cu wire was removed, 9.99 ml of GMA was added, and the solution was stored at 2 - 5 °C until use.

[0078] The concentration of the Cu catalyst in each solution was measured using atomic absorption spectrometry (AAS). The concentration determined from AAS correlated with the UV-VIS peak intensity, and the concentration of the Cu catalyst was easily determined. Figure 7 shows the Cu concentration versus the UV-VIS peak intensity for solutions with different Cu catalyst concentrations.

[0079] Polymerization in 5 / 5 Solution Using 9 mg / mL Activator 5 mL of the 5 / 5 polymerization composition was purged with argon for 3 minutes. Next, 9 mg / mL of NaAsc (activator) was added to the polymerization composition to form a reaction composition together with the activated solid part (glass-like carbon). The reaction composition was stirred with the activated solid part for 40 minutes.

[0080] After polymerization, the solid part coated with the polymer brush was removed from the reaction composition and washed with acetone.

[0081] Polymerization in 5 / 5 Solution with 2 mg / mL Activator 5 mL of the 5 / 5 polymerization composition was purged with argon for 3 minutes. Next, 2 mg / mL of NaAsc (activator) was added to the polymerization composition, thus forming a reaction composition together with the activated solid part (glass-like carbon). The reaction composition was stirred with the activated solid part for 40 minutes.

[0082] After polymerization, the solid part coated with the polymer brush was then removed from the reaction composition and washed with acetone.

[0083] Polymerization in 5 / 5 Solution Using 2 mg / mL Activator 5 mL of the 5 / 5 polymerization composition was purged with argon for 3 minutes. Next, 2 mg / mL of NaAsc (activator) was added to the polymerization composition, thus forming a reaction composition together with the activated solid part (glass-like carbon). The reaction composition was stirred with the activated solid part for 40 minutes.

[0084] After polymerization, the solid part coated with the polymer brush was then removed from the reaction composition and washed with acetone.

[0085] Polymerization in 4 / 5 Solution Using 9 mg / mL Activator 5 mL of the 4 / 5 polymerization composition was purged with argon for 3 minutes. Next, 9 mg / mL of NaAsc (activator) as a powder was added to the polymerization composition, thus forming a reaction composition together with the activated solid part (glass-like carbon). The reaction composition was stirred with the activated solid part for 40 minutes.

[0086] After polymerization, the solid part coated with the polymer brush was then removed from the reaction composition and washed with acetone.

[0087] Polymerization in 4 / 5 Solution Using 5 mg / mL Activator 5 mL of the 4 / 5 polymerization composition was purged with argon for 3 minutes. Next, 5 mg / mL of NaAsc (activator) as a powder was added to the polymerization composition, thus forming a reaction composition together with the activated solid part (glass-like carbon). The reaction composition was stirred with the activated solid part for 40 minutes.

[0088] After coincidence, the solid part coated with the polymer brush was taken out from the reaction composition and washed with acetone.

[0089] Polymerization in 4 / 5 Solution with 2 mg / mL Activating Solution 5 mL of 4 / 5 polymerization composition was purged with argon for 3 minutes. Next, 2 mg / mL of NaAsc (activating solution) was added to the polymerization composition to form a reaction composition together with the activated solid part (glassy carbon). The reaction composition was stirred with the activated solid part for 40 minutes.

[0090] After coincidence, the solid part coated with the polymer brush was taken out from the reaction composition and washed with acetone.

[0091] Polymerization in 3 / 5 Solution Using 9 mg / mL Activator 5 mL of 3 / 5 polymerization composition was purged with argon for 3 minutes. Next, 9 mg / mL of NaAsc (activator) as a powder was added to the polymerization composition to form a reaction composition together with the activated solid part (glassy carbon). The reaction composition was stirred with the activated solid part for 40 minutes.

[0092] After coincidence, the solid part coated with the polymer brush was taken out from the reaction composition and washed with acetone.

[0093] Polymerization in 3 / 5 Solution Using 5 mg / mL Activator 5 mL of 3 / 5 polymerization composition was purged with argon for 3 minutes. Next, 5 mg / mL of NaAsc (activator) as a powder was added to the polymerization composition to form a reaction composition together with the activated solid part (glassy carbon). The reaction composition was stirred with the activated solid part for 40 minutes.

[0094] After coincidence, the solid part coated with the polymer brush was taken out from the reaction composition and washed with acetone.

[0095] Polymerization in 3 / 5 Solution with 2 mg / mL Activator The 3 / 5 polymerization composition of 5 mL was purged with argon for 3 minutes. Next, 2 mg / mL of NaAsc (activator) as a powder was added to the polymerization composition to form a reaction composition together with the activated solid part (glass-like carbon). The reaction composition was stirred with the activated solid part for 40 minutes.

[0096] After polymerization, the solid part coated with the polymer brush was taken out from the reaction composition and washed with acetone.

[0097] Polymerization in 2 / 5 Solution with 9 mg / mL Activating Solution The 2 / 5 polymerization composition of 5 mL was purged with argon for 3 minutes. Next, 9 mg / mL of NaAsc (activator) as a powder was added to the polymerization composition to form a reaction composition together with the activated solid part (glass-like carbon). The reaction composition was stirred with the activated solid part for 40 minutes.

[0098] After polymerization, the solid part coated with the polymer brush was removed from the reaction composition and washed with acetone.

[0099] Polymerization in 2 / 5 Solution Using 5 mg / mL Activator The 2 / 5 polymerization composition of 5 mL was purged with argon for 3 minutes. Next, 5 mg / mL of NaAsc (activator) as a powder was added to the polymerization composition to form a reaction composition together with the activated solid part (glass-like carbon). The reaction composition was stirred with the activated solid part for 40 minutes.

[0100] After polymerization, the solid part coated with the polymer brush was taken out from the reaction composition and washed with acetone.

[0101] Polymerization in 2 / 5 Solution with 2 mg / mL Activator The 2 / 5 polymerization composition of 5 mL was purged with argon for 3 minutes. Next, 2 mg / mL of NaAsc (activator) as a powder was added to the polymerization composition to form a reaction composition together with the activated solid part (glass-like carbon). The reaction composition was stirred with the activated solid part for 40 minutes.

[0102] After coincidence, the solid part coated with the polymer brush was taken out from the reaction composition and washed with acetone.

[0103] Polymerization with 9 mg / mL Activator in 1 / 5 Solution 5 mL of 1 / 5 polymerization composition was purged with argon for 3 minutes. Next, 9 mg / mL of NaAsc (activator) as a powder was added to the polymerization composition to form a reaction composition together with the activated solid part (glass-like carbon). The reaction composition was stirred with the activated solid part for 40 minutes.

[0104] After polymerization, the solid part coated with the polymer brush was taken out from the reaction composition and washed with acetone.

[0105] Polymerization with 5 mg / mL Activator in 1 / 5 Solution 5 mL of 1 / 5 polymerization composition was purged with argon for 3 minutes. Next, 5 mg / mL of NaAsc (activator) as a powder was added to the polymerization composition to form a reaction composition together with the activated solid part (glass-like carbon). The reaction composition was stirred with the activated solid part for 40 minutes.

[0106] After polymerization, the solid part coated with the polymer brush was taken out from the reaction composition and washed with acetone.

[0107] Polymerization with 2 mg / mL Activator in 1 / 5 Solution 5 mL of 1 / 5 polymerization composition was purged with argon for 3 minutes. Next, 2 mg / mL of NaAsc (activation solution) as a powder was added to the polymerization composition to form a reaction composition together with the activated solid part (glass-like carbon). The reaction composition was stirred with the activated solid part for 40 minutes.

[0108] After polymerization, the solid part coated with the polymer brush was removed from the reaction composition and washed with acetone.

[0109] Table 1 shows the polymer brush thickness (nm) of the polymer brushes prepared using GMA monomers with different Cu and NaAsc concentrations.

[0110]

Table 1

[0111] The polymerization composition having a Cu catalyst concentration of 5.5 mg / L was prepared as described below. The polymerization composition was used in the following experiments.

[0112] Effect of Catalyst Concentration and Activator 5 mL of the polymerization composition (1.6, 5.5, 12.3, 27.1, and 70.6 mg / L catalyst, respectively) was added to a test tube equipped with a Teflon magnet and then purged with argon gas for 3 minutes. Subsequently, 2, 5, or 9 mg / mL of NaAsc (activator) was added as a powder. After 20 - 25 seconds (argon gas purge in the headspace), the initiator-terminated sample (glass-like carbon - solid part) was suspended (i.e., the solid part was placed in a suitable holding mechanism and immersed in the reaction composition to avoid contact with the stirring magnet), and the reaction composition was stirred at 500 rpm for 40 minutes to obtain the formation of polymer brushes.

[0113] Thereafter, the obtained polymer brush-coated solid part was flushed with acetone and then sonicated in acetone for 5 minutes as a washing operation.

[0114] Table 2 shows the polymer brush thickness (nm) obtained using the above method for the polymerization of GMA with different known Cu and NaAsc concentrations.

[0115]

Table 2

[0116] Figure 7 shows the Cu catalyst concentration vs. UV-VIS absorbance from AAS for various applied reactants. From the results shown in Figure 7, it became clear that by changing the Cu wire magnet stirring time, it is possible to obtain compositions with different catalyst concentrations.

[0117] Surface Polymerization under 0 - 100% Oxygen Atmosphere 5 mL of the polymerization composition (5.5 mg / L catalyst) was added to a test tube equipped with a Teflon magnet. The polymerization composition was purged with an oxygen / argon gas mixture (O2 concentrations: 0%, 11%, 21% (atmospheric), 34%, 58%, and 100%) for 3 minutes. Subsequently, 25.0 mg of NaAsc (activator) was added to each polymerization composition forming the reaction composition, and after 20 - 25 seconds (accompanied by argon gas purging in the headspace), the initiator-terminated (glass-like carbon - solid part) composition was suspended and added as described above, and the reaction composition was stirred at 500 rpm for various times (5, 10, 20, and 40 minutes respectively) to form polymer brushes.

[0118] After the reaction, here, the solid part coated with the polymer brush was flushed with acetone and subsequently sonicated in acetone for 5 minutes as a washing procedure.

[0119] Figure 8 shows the thickness of the PGMA polymer brushes obtained from polymerizations for various periods under different atmospheric conditions. Figure 8 shows the PGMA polymer brush thickness (nm) obtained by polymerization using a Cu catalyst concentration of 5.5 mg / L and a NaAsc activator concentration of 5 mg / mL under atmospheres with different oxygen contents.

[0120] The results obtained clearly showed that the formation of polymer brushes can be achieved under conditions in a wide range of oxygen contents from 0% to 100% during polymerization.

[0121] Formation of Block Polymer Brushes by Restart of Polymer Brush Samples Using the method for forming polymer brushes described in "Surface Polymerization under 0 - 100% Oxygen Atmosphere", two pre-prepared (under a 21% oxygen atmosphere, see above) PGMA polymer brush-coated glass-like carbon solid parts (polymerized for 5 minutes and 10 minutes respectively) were repolymerized for 10 minutes under a 21% oxygen atmosphere, and GMA was used as the monomer. The polymerization composition and the activator were stored at 2 - 5 °C for 6 - 8 months before being used for the formation of polymer brushes.

[0122] Figure 9 shows the thicknesses of the PGMA polymer brushes after the first and second polymerizations, respectively.

[0123] Furthermore, it was observed that the storage stabilities of the polymerization composition and the activator were excellent. This is because storage for 6 - 8 months before use did not adversely affect the formation of the polymer brush. The polymerization composition and the activator were stored in separate containers. Thus, the expected stability was clearly demonstrated.

[0124] Effect of Catalyst Concentration on Polymerization Rate at 21% Oxygen Content PGMA polymer brush - coated vitreous carbon solid parts were prepared by polymerization at three catalyst concentrations (prepared as described above) under a 21% oxygen atmosphere. The polymerization composition and the activator were stored at 2 - 5 °C for 6 - 8 months before being used for the formation of the polymer brush.

[0125] Figure 10 shows the thicknesses of the PGMA polymer brushes obtained from polymerizations of different times using three different concentrations of catalyst. The PGMA polymer brush thickness (nm) and the NaAsc activator (activator concentration 5 mg / mL under a 21% oxygen atmosphere) for various polymerization times obtained using Cu catalyst concentrations of 1.6, 5.5, and 16.65 mg / L are shown.

[0126] Furthermore, it was observed that the storage stabilities of the polymerization composition and the activator were excellent. This is because storage for 6 - 8 months before use did not adversely affect the formation of the polymer brush. Thus, the expected stability was clearly demonstrated.

[0127] Example 3 Preparation of Polymer Brushes from Methyl Methacrylate (MMA) Preparation of Polymerization Compositions 6 mL of isopropanol and 0.088 mL of N,N,N’,N’’,N’’ - pentamethyldiethylenetriamine (PMDETA - ligand) were stirred for 2 hours and 45 minutes with a Teflon magnet wrapped with a Cu wire. Subsequently, 6 mL of MMA was added to the solution, and the Teflon magnet wrapped with the Cu wire was removed. The resulting polymerization composition was stored at 2 - 5 °C until use.

[0128] Polymerization in Solution 5 mL of the above polymerization composition was purged with argon for 3 minutes. Subsequently, 5 mg / mL of NaAsc (activator) as a powder was added to the polymerization composition to form a reaction composition together with the activated surface. The reaction composition was stirred with the activated solid part (glass-like carbon) for 60 minutes.

[0129] After polymerization, the solid part coated with the polymer brush was taken out of the solution and washed by sonication in HPLC-acetone.

[0130] When the formed polymer brush was examined, it was found that the solid part (glass-like carbon) was evenly coated with the polymer brush.

[0131] Polymerization of MMA on Carbon Fiber A Teflon magnet wrapped with a Cu wire (for forming an activator) was stirred in a solution of 5 mL of iPrOH (solvent) and 0.105 mL of tren (ligand) for 30 minutes. Then, the Teflon magnet wrapped with the copper wire was flushed with HPLC-acetone and transferred to another glass container. Next, 5 mL of MMA (polymerization composition) was added to the solution.

[0132] 5 ml of the above polymerization composition was purged with argon for 3 minutes and heated to 70 °C. Then, 5 mg / mL of NaAsc (activator) as a powder was added to the polymerization composition to form a reaction composition together with the activated surface. The reaction composition was stirred with the activated solid part (carbon fiber) for 120 minutes.

[0133] After polymerization, the solid part coated with the polymer brush was taken out of the reaction composition and washed by sonication in HPLC-acetone.

[0134] Example 4 Further Formation of Polymer Brushes Table 3 shows other monomers that were successfully polymerized on the surface using a method equivalent to that shown previously. The solvent system, dormant transition metal-ligand catalyst, and activator are further disclosed for each monomer.

[0135] Using the method described in the section "Preparation of Polymer Brushes from Glycidyl Methacrylate (GMA) Monomer" of Example 2, a polymerization composition, an activator, and a reaction composition were prepared. Polymer brushes were formed on the solid portion with variations in reaction time and occasional use of a 0% oxygen atmosphere according to the method described in the section "Effect of Catalyst Concentration and Activator" of Example 2.

[0136]

Table 3

[0137] Solvent: DMSO = Dimethyl Sulfoxide H2O = Water iPrOH = Isopropanol MeOH = Methyl Alcohol

[0138] Monomer: A: Styrene B: 2,3,4,5,6-Pentafluorostyrene C: Acrylamide D: 3-Sulfopropyl Methacrylate Potassium Salt E: [2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium Hydroxide F: Poly(ethylene glycol) Methacrylate G: 3-(Fluorosulfonyl)propyl Methacrylate H: Ethylene Glycol Dimethacrylate

[0139] Solid Portion: Alu: Aluminum SS: Stainless Steel GC: Glassy Carbon

[0140] For all samples 1 to 12, the formation of polymer brushes was visually inspected using a combination of water contact angle measurement and ellipsometry. It was observed that the polymer brushes were uniformly distributed, and it was demonstrated that polymer brushes can be formed using a wide range of monomers, solvents, ligands, and activators.

Claims

1. At least one polymerization composition, at least one activator, and one or more monomers provided as one or more of (i) a portion of the polymerization composition, (ii) a portion of the activator, or (iii) a separate composition, A reaction composition for forming a polymer brush on a solid part having a polymerization initiator immobilized on its surface, wherein said at least one polymerization composition is a solvent, one or more transition metal catalysts derived from Cu₂O, CuO, Cu, CuSO₄·5H₂O, or combinations thereof, the transition metal catalysts being in a resting state, a ligand capable of coordinating with the transition metal, and comprising, said ligand being a nitrogen-containing ligand, said activator comprising one or more deoxidizers, A reaction composition, wherein said at least one polymerization composition and said at least one activator are provided as separate compositions.

2. The reaction composition according to claim 1, wherein said one or more deoxidizers are selected from sodium ascorbate, ascorbic acid, hydrazine, hydrazine hydrate, sodium hypophosphite, a mixture of iron powder and sodium chloride, hydrogen carbonate, citric acid, pyrogallic acid, and mixtures thereof.

3. The reaction composition according to claim 1 or 2, wherein said activator further comprises one or more solvents.

4. The reaction composition according to claim 1, wherein said monomer is selected from acrylates, methacrylates, halogen-substituted alkenes, acrylamides, methacrylamides, and styrenes, and mixtures thereof.

5. A reaction composition according to any one of claims 1 to 4, wherein upon mixing the polymerization composition and the activator, a reaction composition is formed that enables the formation of a polymer brush via the polymerization initiator on the surface of the solid part upon contact with the solid part on which the polymerization initiator is immobilized.

6. The reaction composition according to any one of claims 1 to 5, wherein said transition metal catalyst in the resting state is activated by mixing said polymerization composition and said activator.

7. The reaction composition according to claim 1, wherein said activator directly reduces said transition metal catalyst in the resting state to an active transition metal catalyst.

8. The nitrogen-containing ligand is selected from the group consisting of N,N,N',N'',N''' - pentamethyldiethylenetriamine (PMDETA), tris[2-(dimethylamino)ethyl]amine (Me ６ TREN), tris(2-aminoethyl)amine (TREN), tris(2-pyridylmethyl)amine (TPMA), and 2,2'-bipyridyl (BiPy), and the reaction composition according to claim 1.

9. The reaction composition according to claim 3, wherein said solvent is a portion of the polymerization composition, a portion of the activator, or is provided as a separate solution.

10. The reaction composition according to claim 3, wherein the solvent is provided as part of the polymerization composition, part of the activator, and a separate solution.

11. The reaction composition according to claim 1, wherein the concentration of each component is in the range of 0.1 nM to 35 M.

12. The concentration of the monomer is 0.01 M to 5 M, the concentration of the deoxidizer is 0.010 to 0.045 M, and the concentration of the transition metal catalyst in the resting state is 1.0 ppb to 500.0 ppm, The reaction composition according to claim 11.

13. A method for forming a polymer brush on a solid part, comprising: providing the solid part having a polymerization initiator immobilized on the surface; mixing a polymerization composition, an activator, and one or more monomers provided as one or more of (i) part of the polymerization composition, (ii) part of the activator, or (iii) a separate composition to form a reaction mixture, wherein the at least one polymerization composition and the at least one activator are provided as separate compositions; contacting the reaction mixture, which is mixed before contact with the solid part or during contact with the solid part, with the solid part, thereby forming a polymer brush on the surface of the solid part via the polymerization initiator; including the polymerization composition includes a solvent and one or more transition metal catalysts derived from Cu 2 O, CuO, Cu, CuSO 4 *5H 2 O, or a combination thereof, a transition metal catalyst in a resting state, and a ligand capable of coordinating with the transition metal; the ligand is a nitrogen-containing ligand; the method, wherein the activator includes one or more deoxidizers.

14. The method according to claim 13, wherein the solid part is immersed in the reaction mixture.

15. The method according to claim 13, wherein the reaction mixture is sprayed or coated on the solid part.

16. The method according to claim 13, wherein the solid part is contacted with either the polymerization composition or the activator, and then the other of the polymerization composition and the activator is added.

17. The method according to claim 13, wherein the solid part is selected from metals, alloys, glasses, ceramics, plastics, carbon-based materials, and combinations thereof.

18. The method according to claim 17, wherein the carbon-based material is selected from carbon fibers, vitreous carbon, graphene, or graphite.

19. The method according to claim 13, wherein the method is repeated to form another block of the polymer brush on top of the existing layer of the polymer brush.

20. The method according to claim 13, wherein the formation of the polymer brush is carried out under atmospheric conditions.

21. A solvent, One or more transition metal catalysts derived from Cu₂O, CuO, Cu, CuSO₄*5H₂O, or combinations thereof, wherein the transition metal catalyst is in a resting state, A ligand capable of coordinating with the transition metal, A polymerization composition for forming a polymer brush on a solid part having a polymerization initiator immobilized on the surface, which is used in combination with a deoxidizer, The ligand is a nitrogen-containing ligand, The polymerization composition, wherein the transition metal catalyst in the resting state is activated by the deoxidizer.

22. The polymerization composition according to claim 21, further comprising one or more monomers.

23. The polymerization composition according to claim 21, wherein the polymerization composition is in a resting state and no chemical reaction occurs.

24. Upon mixing the polymerization composition and the deoxidizer, when contacting the solid part on which the polymerization initiator is immobilized, a reaction composition containing an activated transition metal catalyst is formed, which enables the formation of a polymer brush via the polymerization initiator on the surface of the solid part. The polymerization composition according to claim 21.

25. The nitrogen-containing ligand is selected from the group consisting of N,N,N',N'',N''' - pentamethyldiethylenetriamine (PMDETA), tris[2-(dimethylamino)ethyl]amine (Me ６ TREN), tris(2-aminoethyl)amine (TREN), tris(2-pyridylmethyl)amine (TPMA), and 2,2'-bipyridyl (BiPy), and the polymerization composition according to claim 21.

26. The polymerization composition according to claim 22, wherein the monomer is selected from acrylates, methacrylates, halogen-substituted alkenes, acrylamides, methacrylamides, and styrenes, and mixtures thereof.

27. The polymerization composition according to claim 21, wherein the concentration of each component ranges from 0.1 nM to 35 M.

28. The concentration of the monomer is from 0.01 M to 5 M, and The concentration of the transition metal catalyst in the state is from 1.0 ppb to 500.0 ppm. The polymerization composition according to claim 27.

29. The polymerization composition according to claim 21, wherein the ligand is present in excess with respect to the transition metal.

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