# US 8,784,635 B2 · Formation of organic electro-grafted films on the surface of electrically conductive or semi-conductive surfaces > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,784,635 B2 - Document ID: US8784635B2 - Status: Granted - Kind: B2 - Application number: 11/711,849 - Filed: 2007-02-28 - Published: 2007-09-13 - Granted: 2014-07-22 - Earliest claimed: 2006-02-28 - Assignees: Alchimer; Alchimedics - Applicants: Christophe Bureau - Inventors: Christophe Bureau - Web page: https://patentgrep.com/patent/US8784635B2 ## CPC - C25D 9/02: with organic materials - A61F 2/82: Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents (stent-grafts for tubular structures of the body other than blood vessels A61F2/04; stent-grafts for blood vessels A61F2/07) - A61L 31/10: Macromolecular materials - A61L 31/14: Materials characterised by their function or physical properties {, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials} - C09D 5/24: Electrically-conducting paints {(conductive materials H01B1/00)} - C09D 5/4476: {comprising polymerisation in situ} - C25D 13/18: using modulated, pulsed, or reversing current - A61F 2210/0076: multilayered, e.g. laminated structures - A61L 2420/04: Coatings containing a composite material such as inorganic/organic, i.e. material comprising different phases - A61L 2420/08: Coatings comprising two or more layers - C09D 5/4407: {with polymers obtained by polymerisation reactions involving only carbon-to-carbon unsaturated bonds} - C09D 5/4419: {with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds} - C09D 5/4423: {Polyesters, esterified polyepoxides} - C09D 5/448: {characterised by the additives used (C09D5/4403 - C09D5/4476, C09D5/4492 take precedence)} - C25D: PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR - A61F: FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS (dental prosthetics A61C) - A61L: METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES (preservation of bodies or disinfecting characterised by the agents employed A01N; preserving, e.g. sterilising, food or foodstuffs A23; preparations for medical, dental or toiletry purposes A61K) - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) ## Abstract The invention relates to a method for grafting an organic film onto an electrically conductive or semiconductive surface by electro-reduction of a solution, wherein the solution comprises one diazonium salt and one monomer bearing at least one chain polymerizable functional group. During the electrolyzing process, at least one protocol consisting of an electrical polarization of the surface by applying a variable potential over at least a range of values which are more cathodic that the reduction or peak potential of all diazonium salts in said solution is applied. The invention also relates to an electrically conducting or semiconducting surface obtained by implementing this method. The invention further relates to electrolytic compositions. ## Claims ### Claim 1 A method for grafting an organic film onto an electrically conductive or semiconductive surface by electro-reduction of a solution, comprising the following steps: a) preparing a solution containing at least one diazonium salt, glycerol, one monomer bearing at least one chain polymerizable functional group, that are precursors of said organic film, and a solvent selected from the group consisting of dimethylformamide, dimethylsulfoxide, ethyl acetate, acetonitrile, tetrahydrofuran, propylene carbonate, dichloroethane and chlorinated solvents, b) electrolyzing said solution in an electrolysis cell using the conducting or semiconducting surface to be coated as working electrode and at least one counterelectrode, so as to result, by application of at least one protocol consisting of an electrical polarization of the surface by applying a variable potential over at least a range of values which are more cathodic than the reduction or peak potential of all diazonium salts in said solution, in a grafted coating of said organic film on said surface. ### Claim 2 (depends on 1) The method according to claim 1, wherein the diazonium salt is an aryldiazonium salt. ### Claim 3 (depends on 1) The method according to claim 1, wherein said monomer is a vinylic monomer. ### Claim 4 (depends on 3) The method according to claim 3, wherein the vinylic monomer is a poly-atomic species bearing a vinylic group. ### Claim 5 (depends on 3) The method according to claim 3, wherein the monomer is an acrylate or a methacrylate. ### Claim 6 (depends on 1) The method according to claim 1, wherein said monomer is a cyclic monomer which undergoes polymerization by nucleophilic attack cleavage. ### Claim 7 (depends on 6) The method according to claim 6, wherein said cyclic monomer is selected from the group consisting of lactic acid, glycolic acid and ε-caprolactone. ### Claim 8 (depends on 1) The method according to claim 1 wherein at least one protocol is applied in cyclic voltammetry scanning (CVS) mode. ### Claim 9 (depends on 1) The method according to claim 1, wherein, in at least one protocol, a variable working current is applied to the surface. ### Claim 10 (depends on 1) The method according to claim 1, wherein the film is obtained by successive application of several protocols selected independently from protocols with variable applied working potential and protocols with variable applied working current, each protocol being applied to the surface for a given duration that is identical to or different from that of the other protocols. ### Claim 11 (depends on 1) The method according to claim 1, wherein the surface is selected from the group consisting of a surface of a noble metal, a surface containing reducible oxide, a graphite surface, a conductive or semiconductive organic surface, a surface of an alloy, a surface of one or more conductive polymer(s), a surface of an intrinsic or doped semiconductor, and combinations thereof. ### Claim 12 (depends on 1) The method according to claim 1, further comprising the step of applying an outer coating. ### Claim 13 (depends on 1) The method according to claim 1, wherein the solvent is dimethylformamide. ### Claim 14 A method for grafting an organic film onto an electrically conductive or semiconductive surface by electro-reduction of a solution, comprising the following steps: a) preparing a solution containing at least one diazonium salt, glycerol, a polymeric or nonpolymeric structure functionalized with at least one vinylic group or cyclic molecule cleavable by nucleophilic attack, that are precursors of said organic film, and a solvent selected from the group consisting of dimethylformamide, dimethylsulfoxide, ethyl acetate, acetonitrile, tetrahydrofuran, propylene carbonate, dichloroethane and chlorinated solvents; b) electrolyzing said solution in an electrolysis cell using the conducting or semiconducting surface to be coated as working electrode and at least one counterelectrode, so as to result, by application of at least one protocol consisting of an electrical polarization of the surface by applying a variable potential over at least a range of values which are more cathodic than the reduction or peak potential of all diazonium salts in the said solution, in a grafted coating of said organic film on said surface. ### Claim 15 (depends on 14) The method according to claim 14, wherein the solvent is dimethylformamide. ### Claim 16 A process of coating a stent with an electro-grafted layer of poly-Hydroxyethylmethacrylate comprising the following steps: Cleaning with Detergent with Ultra-sonic 35 kHz power for 10 to 20 min; Rinsing with DI Water with Ultra-sonic 35 kHz power for 10 to 90 min; Drying; Contacting the stent with cathode of a power supply; Dipping in electrolytic solution comprising: hydroxyethylmethacrylate monomer, at a concentration of 1.5 to 2 mol/l; glycerol, at a concentration of 0.01 to 1 mol/l; dimethyl formamide as the solvent; 4-nitrophenyl diazonium tetrafluoroborate at a concentration of 5×10−4 to 10−1 mol/l; and sodium nitrate (NaNO3) at a concentration of 10−3 to 5×10−2 mol/l; with argon bubbling for 5 to 20 min; Providing in the electrolytic solution an anode connected to the power supply as a counterelectrode; Polarizing stent via a cyclic voltammetry protocol, scanning between 5 and 75 times from open circuit potential to −3 V/CE, where CE is the anode counterelectrode, at a scanning rate of 100 mV/s, with argon bubbling at 8 l/min; First rinsing in DMF with argon bubbling for 5 to 20 min; Second rinsing in DMF with argon bubbling for 5 to 20 min; Rinsing in DI Water for 5 to 20 min; and Drying in Vacuum oven at 40 C.°, 10 mbars for 30 to 180 min. ### Claim 17 A process of coating a stent with an electro-grafted layer of poly-Butylmethacrylate comprising the following steps: Cleaning with Detergent with Ultra-sonic 35 kHz power for 10 to 20 min; Rinsing with DI Water with Ultra-sonic 35 kHz power for 10 to 90 min; Drying; Contacting the stent with cathode of a power supply; Dipping in electrolytic solution comprising: butylmethacrylate monomer, at a concentration of 1.5 to 2 mol/l; glycerol, at a concentration of 0.01 to 1 mol/l; dimethyl formamide as the solvent; 4-nitrophenyl diazonium tetrafluoroborate at a concentration of 5×10−4 to 10−1 mol/l; and sodium nitrate (NaNO3) at a concentration of 10−3 to 5×10−2 mol/l; with argon bubbling for 5 to 20 min; Providing in the electrolytic solution an anode connected to the power supply as a counterelectrode; Polarizing stent via a cyclic voltammetry protocol, scanning between 5 and 75 times from open circuit potential to −3.2 V/CE, where CE is the anode counterelectrode, at a scanning rate of 50 mV/s, with argon bubbling at 8 l/min; First rinsing in DMF with argon bubbling for 5 to 20 min; Second rinsing in DMF with argon bubbling for 5 to 20 min; Rinsing in DI Water for 5 to 20 min; and Drying in Vacuum oven at 40 C.°, 10 mbars for 30 to 180 min. ### Claim 18 A method for grafting an organic film onto an electrically conductive or semiconductive surface by electro-reduction of a solution, comprising the following steps: a) preparing a solution containing at least one diazonium salt, glycerol, a cyclic monomer which undergoes polymerization by nucleophilic attack cleavage, and a solvent selected from the group consisting of dimethylformamide, dimethylsulfoxide, ethyl acetate, acetonitrile, tetrahydrofuran, propylene carbonate, dichloroethane and chlorinated solvents; b) electrolyzing said solution in an electrolysis cell using the conducting or semiconducting surface to be coated as working electrode and at least one counterelectrode, so as to result, by application of at least one protocol consisting of an electrical polarization of the surface by applying a variable potential over at least a range of values which are more cathodic than the reduction or peak potential of all diazonium salts in the said solution, in a grafted coating of said organic film on said surface. ### Claim 19 (depends on 18) The method according to claim 18, wherein the cyclic monomer is chosen from the group consisting of lactic acid, glycolic acid and ε-caprolactone. ### Claim 20 (depends on 18) The method according to claim 18, wherein the solvent is dimethylformamide.