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-9790370-B2
Application number	US-68607607-A
Country	US
Kind code	B2
Filing date	Mar 14, 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 the 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 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, comprising a step of contacting said surface with a liquid solution including:
at least one protic solvent,
at least one adhesion primer,
at least one radically polymerisable monomer, said monomer being different from the adhesion primer,

under non-electrochemical conditions generating radical entities based on the adhesion primer, and wherein the adhesion primer generates said radical entities independent of the surface on which said radical entities are intended to be grafted,
to form an organic film on the surface of the solid support, the organic film being 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 other units are derived from said adhesion primer and from polymerizable monomers.

2. The preparation method of claim 1 , wherein said protic solvent is chosen from the group consisting of water acidified or not, acetic acid, hydroxylated solvents, ethyleneglycol, and mixtures thereof.

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

4. The preparation method of claim 1 , wherein said adhesion primer is a cleavable aryl salt chosen from the group consisting of aryl diazonium salts, aryl ammonium salts, aryl phosphonium salts and aryl sulfonium salts and wherein said aryl group is chosen from aromatic or heteroaromatic carbon structures, consisting of one or more aromatic or heteroaromatic cycles each comprising 3 to 8 atoms, the heteroatom(s) being N, O, P or S.

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

in which:
A represents a monovalent anion and
R represents an aryl group chosen from aromatic or heteroaromatic carbon structures, consisting of one or more aromatic or heteroaromatic cycles each comprising 3 to 8 atoms, the heteroatom(s) being N, O, P or S.

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

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

8. The preparation method of claim 1 , wherein said adhesion primer is chosen 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.

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

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

11. 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 —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.

12. The preparation method of claim 1 , wherein said radically polymerisable monomer is chosen 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.

13. The preparation 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.

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

15. The preparation method of claim 1 , wherein said method includes a preliminary step during which said polymerisable monomer is dispersed or emulsified 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.

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

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

18. The preparation method of claim 1 , wherein said liquid solution also includes one or more chemical initiators.

19. The preparation method of claim 1 , wherein said method includes the following steps, consisting of:
a) adding said at least one monomer to a solution containing said at least one adhesion primer different from said monomer in the presence of said at least one protic solvent,
b) placing the solution obtained in step (a) under said non-electrochemical conditions allowing for the formation of radical entities based on said adhesion primer,
c) placing the surface of the solid support in contact with the solution of step (b).

20. The preparation method of claim 1 , wherein said method includes the following steps, consisting of:
a′) placing the surface of the solid support in contact with a solution containing said at least one adhesion primer in the presence of said at least one protic solvent,
b′) placing the surface of the solid support in contact with the solution of step (a′) under non-electrochemical conditions allowing for the formation of radical entities based on said adhesion primer,
c′) adding said at least one monomer to the solution obtained in step (b′).

21. The preparation method of claim 1 , wherein said method includes an additional step, prior to the film preparation, of cleaning the surface on which the organic film is to be formed.

Assignees

• Mevellec Vincent
• Roussel Sebastien
• Commissariat Energie Atomique

Inventors

• Mevellec Vincent
• Roussel Sebastien

Classifications

• Y10T428/31681

  Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.] · CPC title

• 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

• Y10T428/31616

  Next to polyester [e.g., alkyd] · CPC title

• C08J7/04

  Coating · CPC title