Compositions for forming polymer brushes
View Patent ↗The present invention relates to novel chemical solutions suitable for forming polymer brushes on a surface of a solid part. The present invention further relates to methods of forming polymer brushes on the surface of a solid part using the novel chemical solutions as well as solid parts having polymer brushes coated onto the surface and uses of such solid parts.
1. A reaction composition for forming polymer brushes on a surface of a solid part comprising:
at least one polymerisation composition, and at least one activation agent;
one or more monomers provided as one or more of (i) a part of the polymerisation composition, (ii) a part of the activation agent, or (iii) a discrete composition;
wherein the at least one polymerisation composition comprises one or more dormant transition metal catalysts derived from Cu and Fe and selected from Cu 2 O, CuO, Cu, CuSO 4 *5H 2 O, FeO, Fe 2 O 3 , and Fe 3 O 4 , in combination with a ligand capable of coordinating with the transition metal;
wherein the at least one activation agent comprises one or more oxygen scavengers;
wherein the at least one polymerisation composition and the at least one activation agent are provided as discrete compositions; and
wherein the reaction composition is in contact with the solid part comprising polymerisation initiators immobilised on the surface.
2. The reaction composition according to claim 1 , wherein each of the at least one polymerisation composition and the at least one activation agent can be stored at any suitable temperature until use.
3. The reaction composition according to claim 1 , wherein the one or more oxygen scavengers are selected from sodium ascorbate, ascorbic acid, hydrazine, hydrazine hydrate, sodium hypophosphite, a mixture of iron powder and sodium chloride, hydrogen carbonate, citric acid, and pyrogallic acid, as well as mixtures thereof.
4. The reaction composition according to claim 1 , further comprising one or more solvents.
5. The reaction composition according to claim 1 , wherein the monomers are selected from acrylates, methacrylates, halogen-substituted alkenes, acrylamides, methacrylamides, and styrenes, as well as mixtures thereof.
6. The reaction composition according to claim 1 wherein the reaction composition is formed by mixing the polymerisation composition and the activation agent.
7. The reaction composition according to claim 1 , wherein the at least one dormant transition metal catalyst is activated by mixing the polymerisation composition and the activation agent.
8. A method of forming polymer brushes on a solid part comprising the steps of:
providing the solid part having polymerisation initiators immobilised on a surface of said solid part,
mixing a polymerisation composition and an activation agent, further comprising one or more monomers provided as one or more of (i) part of the polymerisation composition, (ii) part of the activation agent, or (iii) a discrete composition, to form a reaction composition of,
wherein the polymerisation composition comprises one or more dormant transition metal catalysts derived from Cu and Fe and selected from Cu 2 O, CuO, Cu, CuSO 4 *5H 2 O, FeO, Fe 2 O 3 , and Fe 3 O 4 , in combination with a ligand capable of coordinating with the transition metal,
wherein the activation agent comprises one or more oxygen scavengers, and the method further comprises
bringing the reaction composition and the solid part into contact either mixed prior to contact with the solid part, or mixed upon contact with the solid part, thereby initiating surface polymerisation on the solid part, whereby polymer brushes are formed via the polymerisation initiators on the surface of the solid part.
9. The method according to claim 8 , wherein the solid part is immersed into the reaction composition.
10. The method according to claim 8 , wherein the reaction composition is sprayed or painted onto the solid part.
11. The method according to claim 8 , wherein the solid part is brought into contact with either of the polymerisation composition and the activation agent, followed by adding the other of the polymerisation composition and the activation agent.
12. The method according to claim 8 , wherein the solid part is selected from metal, alloy, glass, ceramics, plastics, carbon-based materials such as carbon fibres, glassy carbon, graphene, graphite, and composite materials, and combinations thereof.
13. The method according to claim 8 , wherein the method is repeated in order to form another block of polymer brushes on top of the existing layer of polymer brushes.
14. The method according to claim 8 , wherein the formation of polymer brushes take place under atmospheric conditions.
15. A polymerisation composition, wherein the polymerisation composition comprises:
one or more dormant transition metal catalysts derived from Cu and Fe and selected from Cu 2 O, CuO, Cu, CuSO 4 *5H 2 O, FeO, Fe 2 O 3 , and Fe 3 O 4 , in combination with a ligand capable of coordinating with the one or more dormant transition metal catalysts and one or more monomers;
wherein the dormant transition metal catalyst can be activated on demand by an oxygen scavenger; and
wherein the polymerisation composition is in contact with a solid part comprising polymerisation initiators immobilised thereon.
16. The polymerisation composition according to claim 15 , wherein the polymerisation composition is dormant and such that no chemical reactions can take place.
17. The method according to claim 8 for use in bonding of polymer materials to metals, bonding of functional thermoplastics to glass, bonding of composite fillers functionalized with polymer brushes into the matrix of polymers as composite materials, creating functional surfaces on glasses, metals or plastic materials, creating low friction surfaces on glasses, metals or plastic materials, and creating self-cleaning surfaces on glasses, metals or plastic materials.
18. The reaction composition according to claim 2 , wherein each of the at least one polymerisation composition and the at least one activation agent can be stored at a temperature below 5° C.
19. The reaction composition according to claim 2 , wherein each of the at least one polymerisation composition and the at least one activation agent can be stored at a temperature 8° C.
20. The reaction composition according to claim 1 , wherein the activation agent regenerates the dormant transition metal catalyst into an active transition metal catalyst.
21. The reaction composition according to claim 1 , wherein the ligand is a nitrogen-containing ligand.
22. The reaction composition according to claim 21 , wherein 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′-bipyridil (BiPy).
23. The reaction composition according to claim 4 , wherein the solvent is part of the polymerisation composition, part of the activation agent, or provided as a discrete solution.
24. The reaction composition according to claim 4 , wherein the solvent is part of the polymerisation composition, part of the activation agent, and provided as a discrete solution.
25. The reaction composition according to claim 4 , wherein a concentration of each component relative to the one or more solvents is in the range of from 0.1 nM to 35 M.
26. The reaction composition according to claim 24 , wherein:
the monomer concentration relative to the solvent is from 0.01 M to 5 M;
the oxygen scavenger concentration relative to the solvent is from 0.01 M to 0.045 M; and
the dormant transition metal catalyst concentration relative to the solvent is from 1.0 ppb to 500.0 ppm.
27. The reaction composition according to claim 1 , wherein the polymerisation composition and other solutions or components are mixed prior to contact with a solid part, or mixed upon contact with a solid part.
28. The polymerisation composition according to claim 15 , further comprising one or more solvents.
29. The polymerisation composition according to claim 15 , wherein the polymerisation composition is stored at a temperature below 5° C.
30. The polymerisation composition according to claim 15 , wherein the polymerisation composition is stored at a temperature below 8° C.
31. The polymerisation composition according to claim 15 , wherein the one or more oxygen scavengers are selected from sodium ascorbate, ascorbic acid, hydrazine, hydrazine hydrate, sodium hypophosphite, a mixture of iron powder and sodium chloride, hydrogen carbonate, citric acid, and pyrogallic acid, as well as mixtures thereof.
32. The polymerisation composition according to claim 15 , wherein the ligand is a nitrogen-containing ligand.
33. The polymerisation composition according to claim 31 , wherein 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-pyridyl-methyl)amine (TPMA), and 2,2′-bipyridil (BiPy).
34. The polymerisation composition according to claim 15 , wherein the one or more monomers are selected from acrylates, methacrylates, halogen-substituted alkenes, acrylamides, methacrylamides, and styrenes, as well as mixtures thereof.
35. The polymerisation composition according to claim 31 , wherein a concentration of each component relative to the solvent is in the range of from 0.1 nM to 35 M.
36. The polymerisation composition according to claim 34 , further comprising one or more solvents, wherein:
a concentration of the one or more monomers relative to the one or more solvents is from 0.01 M to 5 M; and
the dormant transition metal catalyst concentration relative to the one or more solvents is from 1.0 ppb to 500.0 ppm.