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-9790371-B2
Application number	US-75339407-A
Country	US
Kind code	B2
Filing date	May 24, 2007
Priority date	Dec 19, 2006
Publication date	Oct 17, 2017
Grant date	Oct 17, 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 protic solvent, (ii) at least one adhesion primer, and (iii) at least one monomer different from the adhesion primer and radically polymerisable, under non-electrochemical conditions, and allowing the formation of radical entities based on the adhesion primer. 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 a surface of a solid support under non-electrochemical conditions, comprising contacting the surface of the solid support with a liquid solution comprising:
at least one protic solvent,
at least one adhesion primer,
at least one radically polymerizable monomer, said monomer being different from the adhesion primer,
under non-electrochemical conditions generating radical entities based on the adhesion primer, where the adhesion primer generates said radical entities independent of the surface on which said radical entities are intended to be grafted,
and wherein the surface of the solid support contacted with said liquid solution comprising at least one area covered with a mask to form an organic film covalently grafted on the surface of the solid support, said organic film being polymeric or copolymeric and having a monomer unit sequence in which a first unit is bonded to the solid support and is a derivative of the adhesion primer and the other units are derived from said adhesion primer and from polymerizable monomers.

2. The method of claim 1 , wherein said protic solvent is water, optionally acidified, acetic acid, hydroxylated solvents, or ethyleneglycol, and mixtures thereof.

3. The method of claim 1 , wherein said adhesion primer is a cleavable aryl salt selected from the group consisting of aryl diazonium salt, aryl ammonium salt, aryl phosphonium salt and aryl sulfonium salt.

4. The method of claim 1 , wherein said adhesion primer is a cleavable aryl salt selected from the group consisting of aryl diazonium salt, aryl ammonium salt, aryl phosphonium salt and aryl sulfonium salt and wherein said aryl group comprises an aromatic or heteroaromatic carbon structure, optionally mono- or polysubstituted with at least one substituent, said aromatic or heteroaromatic carbon structure comprising at least one aromatic or heteroaromatic cycle comprising 3 to 8 atoms, said aromatic or heteroaromatic cycle comprising at least one N, O, P or S heteroatom, and the substituent comprising at least one heteroatom or C1 to C6 alkyl group.

5. The method of claim 1 , wherein said adhesion primer is a cleavable aryl salt represented by formula (I):
R—N 2 + ,A −   (I)

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

6. The method of claim 1 , wherein said adhesion primer is a cleavable aryl salt represented by formula (I):
R—N 2 + ,A −   (I)

in which:
A represents a monovalent anion and
R represents an aryl group selected from the group consisting of aromatic or heteroaromatic carbon structure, optionally mono- or polysubstituted with at least one substituent, the aromatic or heteroaromatic carbon structure comprising at least one aromatic or heteroaromatic cycle comprising 3 to 8 atoms, the aromatic or heteroaromatic cycle comprising at least one N, O, P or S heteroatom, and the substituent comprising at least one heteroatom or C 1 to C 6 alkyl group.

7. The method of claim 6 , wherein the aromatic or heteroaromatic carbon structures are mono- or polysubstituted with one or more heteroatoms or C 1 to C 6 alkyl groups.

8. The method of claim 1 , wherein said adhesion primer is a cleavable aryl salt represented by formula (I):
R—N 2 + ,A −   (I)

in which:
A represents a monovalent anion selected from the group consisting of an inorganic anion, a halogen borate and an organic anion, and
R represents an aryl group.

9. The method of claim 1 , wherein said adhesion primer is selected from the group consisting of 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.

10. The method of claim 1 , wherein said adhesion primer concentration in said liquid solution is between around 10 −6 and 5 M.

11. The method of claim 1 , wherein said radically polymerizable monomer is a molecule comprising at least one ethylene bond.

12. The 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 —COOR 5 group in which R 5 represents a hydrogen atom or a C 1 -C 12 alkyl group, a nitrile, a carbonyl, an amine or an amide.

13. The method of claim 1 , wherein said radically polymerisable monomer is selected from the group consisting of vinyl acetate, acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate, butyl methacrylate, propyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate and their derivatives; acrylamides, cyanoacrylates, di-acrylates and di-methacrylates, tri- acrylates and tri-methacrylates, tetra-acrylates and tetra methacrylates, styrene, parachloro-styrene, pentafluoro-styrene, N-vinyl pyrrolidone, 4-vinyl pyridine, 2- vinyl pyridine, vinyl halides, di-vinylbenzene (DVB), and vinyl cross-linking agents based on acrylate, methacrylate and derivatives thereof.

14. The method of claim 1 , wherein the amount of said radically polymerisable monomer represents between 18 and 40 times the solubility of said monomer at room temperature in the liquid solution.

15. The method of claim 1 , wherein said liquid solution also comprises at least one surfactant.

16. The method of claim 1 , wherein said method further comprises dispersing or emulsifying said polymerizable monomer in the presence of at least one surfactant, or by ultrasound, before it is mixed with the at least one protic solvent and the at least one adhesion primer.

17. The method of claim 1 , wherein the non-electrochemical conditions allowing for the formation of radical entities are selected from the group consisting of thermal, kinetic, chemical, photochemical or radiochemical conditions and a combination thereof, to which the adhesion primer is subjected.

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

19. The method of claim 1 , wherein said liquid solution further comprises at least one chemical initiator.

20. The method of claim 1 , wherein said method comprises:
adding said at least one monomer to a solution comprising said at least one adhesion primer different from said monomer in the presence of said at least one protic solvent and optionally at least one chemical initiator to produce a second solution,
placing the second solution under said non-electrochemical conditions allowing for the formation of radical entities based on said adhesion primer and possibly based on said chemical initiator, to produce a third solution,
placing the surface of the solid support in contact with the third solution.

21. The method of claim 1 , wherein said method comprises:
placing the surface of the solid support in contact with a solution comp

Assignees

• Mevellec Vincent
• Roussel Sébastien
• Palacin Serge
• Commissariat Energie Atomique

Inventors

• Mevellec Vincent
• Roussel Sébastien
• Palacin Serge

Classifications

• H01L51/0006

  Electricity · mapped topic

• C09D4/00 Primary

  Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16} · CPC title

• H01L51/0075

  Electricity · mapped topic

• C08J7/04

  Coating · CPC title

• H10K85/701

  Langmuir Blodgett films · CPC title