Method for preparing an organic film at the surface of a solid support under non-electrochemical conditions, solid support thus obtained and preparation kit

Patent metadata

Field	Value
Publication number	US-9725602-B2
Application number	US-96010907-A
Country	US
Kind code	B2
Filing date	Dec 19, 2007
Priority date	Dec 19, 2006
Publication date	Aug 8, 2017
Grant date	Aug 8, 2017

Abstract

This invention relates to a method for preparing an organic film at the surface of a solid support, with a step of contacting said surface with a liquid solution including (i) at least one solvent, (ii) at least one adhesion primer, under non-electrochemical conditions, and allowing the formation of radical entities based on the adhesion primer. The liquid solution can also include (iii) at least one monomer different from the adhesion primer and radically polymerizable. This invention also relates to a non-electrically-conductive solid support on which an organic film according to said method is grafted, and a kit for preparing an essentially polymeric organic film at the surface of a solid support.

First claim

The invention claimed is:

1. A method for preparing an organic film at the surface of a solid support, wherein it includes a step of contacting said surface with a liquid solution including:
at least one aprotic solvent,
at least one cleavable aryl salt and
at least one radically polymerisable monomer different from said cleavable aryl salt, said organic film being polymeric or copolymeric and having a monomer unit sequence in which the first unit is constituted by a derivative of the cleavable aryl salt and the other units are derived from said cleavable aryl salt and from polymerizable monomers, wherein said contacting is under non-electrochemical conditions enabling formation of radical entities based on the cleavable aryl salt, wherein the cleavable aryl salts generate said radical entities without reacting with the surface on which said radical entities are intended to be grafted.

2. The preparation method of claim 1 , wherein said aprotic solvent is chosen from the group constituted by dimethylformamide (DMF), acetone and dimethyl sulfoxide (DMSO).

3. The preparation method of claim 1 , wherein said cleavable aryl salt is chosen from the group constituted by aryl diazonium salts, aryl ammonium salts, aryl phosphonium salts and aryl sulfonium salts.

4. The preparation method of claim 1 , wherein said cleavable aryl salt is chosen from the group constituted by aryl diazonium salts, aryl ammonium salts, aryl phosphonium salts and aryl sulfonium salts and wherein said aryl group is chosen from the aromatic or heteroaromatic carbon structures, possibly mono- or polysubstituted, constituted by one or more aromatic or heteroaromatic cycles each comprising 3 to 8 atoms, the heteroatom(s) being capable of being N, O, P or S, and the substituent(s) possibly containing one or more heteroatoms or alkyl groups in C 1 to C 6 .

5. The preparation method of claim 1 , wherein said cleavable aryl salt has the following formula (I):
R—N 2 + ,A −   (I)

in which:
A represents a monovalent anion and
R represents an aryl group.

6. The preparation method of claim 1 , wherein said cleavable aryl salt has the following formula (I):
R—N 2 + ,A −   (I)

in which:
A represents a monovalent anion and
R represents an aryl group chosen from the aromatic or heteroaromatic carbon structures, possibly mono- or polysubstituted, constituted by one or more aromatic or heteroaromatic cycles each comprising 3 to 8 atoms, the heteroatom(s) being capable of being N, O, P or S, and the substituent(s) possibly containing one or more heteroatoms or alkyl groups in C 1 to C 6 .

7. The preparation method of claim 1 , wherein said cleavable aryl salt has the following formula (I):
R—N 2 + ,A −   (I)

in which:
A represents a monovalent anion chosen from the inorganic anions, the halogenborates and the organic anions and
R represents an aryl group.

8. The preparation method of claim 1 , wherein said cleavable aryl salt is chosen from the group constituted by phenyldiazonium tetrafluoroborate, 4-nitrophenyldiazonium tetrafluoroborate, 4-bromophenyldiazonium tetrafluoroborate, 4-aminophenyldiazonium chloride, 2-methyl-4-chlorophenyldiazonium chloride, 4-benzoylbenzenediazonium tetrafluoroborate, 4-cyanophenyldiazonium tetrafluoroborate, 4-carboxyphenyldiazonium tetrafluoroborate, 4-acetamidophenyldiazonium tetrafluoroborate, 4-phenylacetic acid diazonium tetrafluoroborate, 2-methyl-4-[(2-methylphenyl)diazenyl]benzenediazonium sulphate, 9,10-dioxo-9,10-dihydro-1-anthracenediazonium chloride, 4-nitronaphthalenediazonium tetrafluoroborate and naphthalenediazonium tetrafluoroborate.

9. The preparation method of claim 1 , wherein said cleavable aryl salt concentration in said liquid solution is between around 10 −6 and 5 M.

10. The preparation method of claim 1 , wherein said cleavable aryl salt is prepared in situ in said liquid solution.

11. The preparation method of claim 1 , wherein said liquid solution also contains at least one surfactant.

12. The preparation method of claim 1 , wherein the non-electrochemical conditions allowing for the formation of radical entities are chosen from the group constituted by thermal, kinetic, chemical, photochemical or radiochemical conditions and a combination thereof, to which the cleavable aryl salt is subjected.

13. The preparation method of claim 1 , wherein the non-electrochemical conditions allowing for the formation of radical entities are chemical conditions.

14. The preparation method of claim 1 , wherein said liquid solution also includes one or more chemical initiator(s).

15. The preparation method of claim 1 , wherein said liquid solution also includes one or more chemical initiator(s) chosen from:
a reducing metal in a finely divided form,
a metallocene,
an organic or inorganic base in proportions sufficient for the pH of the liquid solution to be greater than or equal to 4,
a pre-irradiated polymeric matrix.

16. The preparation method of claim 1 , wherein the surface of said solid support has at least one atom capable of being involved in a radical reaction.

17. The preparation method of claim 1 , wherein said solid support and/or the surface of said solid support are made of a material chosen from the group constituted by metals, wood, paper, cotton, felt, silicon, carbon nanotubes, fluoro-polymers and diamond.

18. The preparation method of claim 1 , wherein the surface of the solid support contacted with said liquid solution comprises at least one area covered with a mask.

19. The preparation method of claim 1 , wherein the surface of the solid support contacted with said liquid solution comprises at least one area covered with a mask and wherein the mask is not soluble in the solvent of said liquid solution.

20. The preparation method of claim 1 , wherein the surface of the solid support contacted with said liquid solution comprises at least one area covered with a mask composed of alkylthiols.

21. The preparation method of claim 1 , wherein said radically polymerisable monomer is a molecule comprising at least one ethylene-type bond.

22. The preparation method of claim 1 , wherein said radically polymerisable monomer is a molecule with the following formula (II):

in which the R 1 to R 4 groups, identical or different, represent a non-metallic monovalent atom, a hydrogen atom, a saturated or unsaturated chemical group, a —COOR 5 group in which R 5 represents a hydrogen atom or an alkyl group in C 1 -C 12 , a nitrile, a carbonyl, an amine or an amide.

23. The preparation method of claim 1 , wherein said radically polymerisable monomer is chosen from the group constituted by vinyl acetate, acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate, butyl methacrylate, propyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate and their derivatives; the acrylamides, aminoethyl, propyl, butyl, pentyl and hexyl methacrylamides, the cyanoacrylates, the di-acrylates and di-methacrylates, the tri-acrylates and tri-methacrylates, the tetra-acrylates and tetra-methacrylates tetramethacrylate pentaerythritol, styrene and its derivatives, parachloro-styrene, pentafluoro-styrene, N-vinyl pyrrolidone, 4-vinyl pyridine, 2-vinyl pyridine, the vinyl halides, acryloyl or methacryloyl, di-vinylbenzene (DVB), and vinyl cross-linking agents based on acrylate, methacry

Assignees

• Mevellec Vincent
• Roussel Sebastien
• Palacin Serge
• Deniau Guy
• Berthelot Thomas
• Baudin Cecile
• Trenggono Adhitya
• Commissariat Energie Atomique

Inventors

• Mevellec Vincent
• Roussel Sebastien
• Palacin Serge
• Deniau Guy
• Berthelot Thomas
• Baudin Cecile
• Trenggono Adhitya

Classifications

• H01L51/0006

  Electricity · mapped topic

• Y10T428/31989

  Of wood · CPC title

• H01L51/0075

  Electricity · mapped topic

• Y10T428/26

  Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension · CPC title

• Y10T428/31504

  Composite [nonstructural laminate] · CPC title