EP1509480A1 - Method for the production of a mineral substrate with modified surface and substrate thus obtained - Google Patents

Method for the production of a mineral substrate with modified surface and substrate thus obtained

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Publication number
EP1509480A1
EP1509480A1 EP03755999A EP03755999A EP1509480A1 EP 1509480 A1 EP1509480 A1 EP 1509480A1 EP 03755999 A EP03755999 A EP 03755999A EP 03755999 A EP03755999 A EP 03755999A EP 1509480 A1 EP1509480 A1 EP 1509480A1
Authority
EP
European Patent Office
Prior art keywords
substrate
mineral substrate
organic
silica
organotrihydrosilane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP03755999A
Other languages
German (de)
French (fr)
Inventor
Gérard LANNEAU
Michel Granier
Johanne Moineau
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Universite Montpellier 2 Sciences et Techniques
Original Assignee
Centre National de la Recherche Scientifique CNRS
Universite Montpellier 2 Sciences et Techniques
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Application filed by Centre National de la Recherche Scientifique CNRS, Universite Montpellier 2 Sciences et Techniques filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP1509480A1 publication Critical patent/EP1509480A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the present invention relates to a process for the preparation of a mineral substrate modified at the surface by organic groups, as well as the modified substrates obtained.
  • SAMs Self-assembled monolayers
  • These SAMs monolayers have great stability and resistance to various disturbances, in particular to corrosion or to the presence of solvents, because the organic molecules are fixed to the silica by covalent bonds.
  • Various techniques for grafting an organic layer onto the surface of a silica substrate are known: organization of the layer by physisorption, for example grafting an alkane onto a gold or silver substrate, from alkane thiols; organization of the layer by chemisorption, for example grafting of an alkane onto a platinum substrate from alcohols or amines, or onto alumina substrate from carboxylic acid; grafting of organic groups onto a substrate comprising surface OH groups, by covalent bonding from organosilanes such as alkylchlorosilanes, alkylalkoxysilanes or alkylaminosilanes (cf. in particular A. Ulman, Chem.
  • organosilanes such as alkylchlorosilanes, alkylalkoxysilanes or alkylaminosilanes
  • the object of the present invention is to provide a process for obtaining surface-modified silica substrates by depositing a dense, homogeneous and well-organized layer.
  • the process according to the invention consists in bringing a mineral substrate carrying silanol functions on its surface into contact with a solution of an organotrihydrosilane in an organic solvent, at a temperature below 30 ° C.
  • a wafer-type silicon substrate carrying a layer of silica on its surface can be obtained by various methods.
  • a first method consists in removing the native silica layer by soaking the silicon substrate in an HF solution containing at least 10% by volume of HF in ultra-pure water under ultrasound, rinsing with ultrapure water. , then treat with ozone under UV.
  • Such treatment which is particularly preferred, is described in particular by JR Vig, J. Vac. Sci. Technol., 1985, 3, 1027-1034.
  • a second method consists in subjecting said silicon substrate to a flow of oxygen at a high temperature, for example at 1150 ° C., as described in particular by DL Angst, Langmuir, 1991, 7, 2236-2242.
  • the silicon substrate is subjected to chemical oxidation by the basic route: after cleaning the surface of the substrate with a solvent under ultrasound, the substrate is left in a mixture H 2 0, NH 4 OH, H 2 0 2 5/1/1, then rinsed with deionized water, dried and rehydrated (Cf. for example "JD Legrange, et al., Langmuir, 1993, 9, 1749-1753").
  • the silicon substrate is subjected to an acidic chemical oxidation: the substrate is cleaned with a basic solution, then immersed in an acid mixture of the H 2 S0 4 / H 2 ⁇ 2 type (Cf. AK Kakkar , et al., Langmuir, 1998, 14, 6941-6947).
  • the actual grafting step that is to say bringing the organotrihydrosilane into contact with the silica substrate, is carried out in a neutral atmosphere (preferably under argon), using an organotrihydrosilane solution in a aprotic solvent.
  • aprotic solvents it is preferable to use those which have a low hygroscopic character.
  • the organotrihydrosilane can be chosen from the compounds XE-SiH 3 in which E is a spacer segment and X represents H or a reactive terminal function.
  • X can be chosen from any function capable of allowing the attachment of other organic groups (for example an inated group, a halogen, an epoxy, a pyridyl, an ester, a tosylate (p-toluenesulfonyl), a hetero- cumulene (such as an isocyanate, isothiocyanate or carbodiimide) or a metal complexing agent (for example a crown ether, a cryptand, a calixarene which is a macrocycle obtained by condensation of a phenolic derivative with formaldehyde).
  • organic groups for example an inated group, a halogen, an epoxy, a pyridyl, an ester, a tosylate (p-toluenesulfonyl), a hetero
  • the spacer group E makes it possible to confer particular properties on the film obtained by implementing the method.
  • Group E is chosen from the radicals making it possible to obtain an organized monolayer.
  • a long chain alkylene type E radical allows interchain interaction.
  • the radicals E of the alkylene type very particularly preferred are those which have from 8 to 24 carbon atoms.
  • a radical E comprising two triple bonds -C ⁇ C- allows crosslinking.
  • a radical E comprising a conjugated aromatic chain confers non-linear optical properties.
  • a radical E of the pyrrole, thiophene or polysilane type confers electronic conduction.
  • a radical E of the heterosubstituted polyaromatic type confers photo / electroluminescence properties.
  • a radical E of the heterosubstituted polyaromatic type confers photo / electroluminescence properties.
  • a group E of the alkyl or fluoroalkyl type in particular an alkyl or fluoroalkyl group having from 3 to 24 carbon atoms, makes it possible to use the layers obtained in chromatography or in electrophoresis.
  • the organotrihydrosilane solution preferably contains from 10 ⁇ 3 to 10 "1 mole / 1. Solutions in which the concentration of organotrihydroxilane is of the order of 10 -2 mole / 1 are particularly preferred.
  • the duration of the grafting is preferably between 4 and 24 hours, a duration of around 12 hours allows good results to be obtained.
  • the reaction medium must be maintained at a temperature below 30 ° C.
  • the limit value depends on the substituent XE-. This limit value tends to decrease when the number of carbon atoms of the substituent decreases. The determination of the limit value for a given substituent is within the reach of the man of job. Useful information can be found in particular in Brzoska et al, (Langmuir, 1994, 10, 4367), which mentions the existence of a critical temperature Te controlling the quality of the self-assembled monolayers obtained from different alkyltrichlorosilanes.
  • the limit temperature is generally less than 30 ° C. For example, the temperature must be less than 30 ° C if R is C ⁇ sH 37 and less than 10 ° C if R is C ⁇ 2 H 25 .
  • organosilane XE-SiH 3 as a coupling agent allows the initial formation of an Si-O-Si bond by direct condensation between the Si-H function of the reagent with a Si-OH silanol function carried by the surface. of the substrate. This grafting method considerably limits the formation of aggregates, which are detrimental to the deposition of a homogeneous layer.
  • the use of XE-SiH 3 also has the advantage of producing easily eliminated by-products, namely H 2 . There is no risk of finding anionic entities or protic compounds inherent in the processes of the prior art using chlorosilanes or alkoxysilanes on the treated substrate.
  • the silica substrate modified according to the method of the present invention comprises on its surface a monolayer of XE- segments fixed by covalent Si-O-Si bond, said layer comprising X functions uniformly distributed over the surface and accessible.
  • the method of the invention consists in depositing an organic monolayer on a surface layer of initially very hydrophilic silica, the contact angle being less than 10 °. After grafting, the wettability of the o
  • FIG. 1 illustrates the state of a drop of water on a hydrophilic surface, the angle ⁇ being less than 90 °.
  • FIG. 2 illustrates the state of a drop of water on a hydrophobic surface, the angle ⁇ being greater than 90 °.
  • the images obtained by AFM show that the surface is homogeneous and has a very low average surface roughness (RMS), generally less than 0.2 nm.
  • RMS average surface roughness
  • the roughness of the treated substrate is independent of the nature of the grafted organic group, it remains very close to that of the initial untreated substrate.
  • the substrate coated with a monolayer obtained by the proposed process is generally characterized by a good recovery rate and a good organization of the chains on its surface.
  • the covalent bond by which the substrate is attached to the organic group is of the -SiH 2 O-Si- type.
  • the presence of SiH 2 groups is revealed by the si-H vibration band at 2150 cm -1 . This band is not found on the substrates modified according to the methods of the prior art using an alkyltrichlorosilane or an alkyltrialkoxysilane comprising the same alkyl group.
  • the present invention is described in more detail with the aid of the following examples, to which it is not however limited.
  • Example 1 A series of silicon substrates coated with an organic layer were prepared by treatment with octadecyl trihydrosilane.
  • cut silicon disks (1,0,0) were used to obtain rectangular plates of 1 x 2 cm 2 .
  • each wafer was soaked in a concentrated HF solution for a few seconds, until the surface became completely hydrophobic. Then, each plate was rinsed with ultra-pure water, then treated with ozone under UV.
  • Each plate thus treated was immediately introduced into a Schlenck tube containing 20 ml of a 10 ⁇ 2 M solution of octadecyltrihydrosilane in CC1 4 , and kept in the tube for 24 h at a temperature of 15 ° C, without shaking. .
  • the platelets were extracted from the Schlenck tubes, washed with CCl 4 , with absolute ethanol, then with chloroform, each washing being carried out under ultrasound, for a period of the order of 5 min.
  • the platelets thus obtained can be stored in an ambient atmosphere, without undergoing degradation.
  • the contact angle on the surface of the platelets is 98 ° ⁇ 2, which indicates a hydrophobic and homogeneous surface.
  • silicon wafers were treated with octadecyltrichlorosilane, for comparison.
  • the substrates treated according to the invention have a Vsi-H band at 2150 cm "1 which does not exist for the substrates obtained from C ⁇ 8 H 37 SiCl 3 and which corresponds to the existence of Si-H bonds in a type environment
  • the images obtained in AFM for the wafers of the invention show a homogeneous surface with a very low roughness, of the order of 0.15 - 0.20 nm.
  • Example 3 The procedure of Example 1 was reproduced using octadecyltrihydrosilane, only changing the reaction temperature in the Schlenck tube. Two series of tests were carried out at 5 ° C and 20 ° C respectively. The analyzes carried out on the platelets gave identical results.
  • Example 3 The procedure of Example 1 was reproduced using octadecyltrihydrosilane, only changing the reaction temperature in the Schlenck tube. Two series of tests were carried out at 5 ° C and 20 ° C respectively. The analyzes carried out on the platelets gave identical results.
  • Example 3 The procedure of Example 1 was reproduced using octadecyltrihydrosilane, only changing the reaction temperature in the Schlenck tube. Two series of tests were carried out at 5 ° C and 20 ° C respectively. The analyzes carried out on the platelets gave identical results.
  • Example 3 The procedure of Example 1 was reproduced using octadecyltrihydrosilane, only changing the reaction temperature in the Schl
  • Example 1 The procedure of Example 1 was reproduced, but replacing the octadecytrihydrosilane with phenyltrihydrosilane, all the other conditions being identical.
  • the contact angle measured on the surface of the modified inserts is 74 ° ⁇ 4.
  • the images obtained in AFM for the wafers of the invention show a homogeneous surface with a very low roughness, of the order of 0.2 nm.
  • FIG. 3 illustrates the surface condition of the wafer after grafting of p-methylstilbényltrihydrosilane.
  • the contact angle measured on the surface of the modified inserts is 85 ° + 3.
  • the images obtained in AFM for the platelets show a homogeneous surface with a very low roughness, of the order of 0.2 nm.
  • the contact angle measured on the surface of the modified wafers is 75 ° + 4.
  • the images obtained in AFM for the platelets show a homogeneous surface with a very low roughness, of the order of 0.2 nm.
  • FIG. 4 illustrates the surface condition of the wafer after the post-grafting reaction of p-bromotoluene.
  • the platelets thus obtained can be stored in an ambient atmosphere, without undergoing degradation.
  • the method according to the invention has been implemented for a silica substrate in the form of colloidal silica.
  • the substrate is an activated silica sold by the company Merck under the name Silica Merck 60F.
  • 0.5 g of the activated silica was treated with 1 g of octadecyltrihydrosilane in 20 ml of CCl 4 at 19-20 ° C for 24 h with magnetic stirring.
  • the powder obtained was filtered, washed 2 times with 20 ml of CC1 4 , then 4 times with 20 ml of THF to remove any physisorbed silanes.
  • grafted silane is characterized by infrared and NMR spectroscopy.
  • An IR band at 2165 cm ⁇ 1 and a signal at -31 ppm in NMR 29 Si show the presence of -0-SiR (H) -0- functions. This result supposes the hydrolysis of a consecutive Si-H bond fixing the organosilane on the surface.

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Abstract

The invention relates to a method for the production of a mineral substrate with surface modified by organic groups. Said method comprises placing the surface of a mineral substrate with silanol functional groups in contact with a solution of an organotrihydrosilane in an organic solvent at a temperature of less than 30 °C. The mineral substrate with silanol functions can comprise silica particles, a sheet of glass, quartz or mica as well as silicon of the wafer type covered by a layer of silica deposited by an appropriate preliminary treatment.

Description

Procédé pour l'élaboration d'un substrat minéral modifié en surface, et substrat obtenu Process for the preparation of a surface-modified mineral substrate, and substrate obtained
La présente invention concerne un procédé pour l'élaboration d'un substrat minéral modifié en surface par des groupes organiques, ainsi que les substrats modifiés obtenus .The present invention relates to a process for the preparation of a mineral substrate modified at the surface by organic groups, as well as the modified substrates obtained.
L'utilisation d'agents de couplage, qui permettent d'améliorer l'adhésion entre une matrice organique et un substrat inorganique par formation d'un film intermédiaire est de plus en plus répandue. Les monocouches auto-assemblées, appelées SAMs (pour self assembled onolayers) , qui sont formées par des molécules organiques à longues chaînes aliphatiques sur un substrat de silice constituent une alternative aux films formés par physisorption selon la technique de Langmuir-Blodgett. Ces monocouches SAMs possèdent une grande stabilité et une résistance à différentes perturbations, notamment à la corrosion ou à la présence de solvants, du fait que les molécules organiques sont fixées sur la silice par des liaisons covalentes. Diverses techniques de greffage d'une couche organique à la surface d'un substrat de silice sont connues : organisation de la couche par physisorption, par exemple greffage d'un alcane sur un substrat or ou argent, à partir d'alcane- thiols ; organisation de la couche par chimisorption, par exemple greffage d'un alcane sur un substrat de platine à partir d'alcools ou d'aminés, ou sur substrat d'alumine à partir d'acide carboxylique ; greffage de groupes organiques sur un substrat comportant des groupes OH de surface, par liaison covalente à partir d' organosilanes tels que des alkylchlorosilanes, des alkylalcoxysilanes ou des alkyl- aminosilanes (Cf. notamment A. Ulman, Chem. Rev., 1996, 96, 1533-1554). Dans un procédé de greffage de groupes organiques sur un substrat de silice portant des groupes Si-OH, à partir d' organotrichlorosilanes, il se forme de l'acide chlorhydrique qui catalyse aussi bien la réaction d'hydrolyse qui provoque la fixation de 1 ' organosilane à la surface du substrat, que 1 ' homocondensation des organosilanes entre eux. Le processus global est ainsi accéléré au détriment deThe use of coupling agents, which make it possible to improve the adhesion between an organic matrix and an inorganic substrate by the formation of an intermediate film, is more and more widespread. Self-assembled monolayers, called SAMs (for self-assembled onolayers), which are formed by organic molecules with long aliphatic chains on a silica substrate constitute an alternative to films formed by physisorption according to the Langmuir-Blodgett technique. These SAMs monolayers have great stability and resistance to various disturbances, in particular to corrosion or to the presence of solvents, because the organic molecules are fixed to the silica by covalent bonds. Various techniques for grafting an organic layer onto the surface of a silica substrate are known: organization of the layer by physisorption, for example grafting an alkane onto a gold or silver substrate, from alkane thiols; organization of the layer by chemisorption, for example grafting of an alkane onto a platinum substrate from alcohols or amines, or onto alumina substrate from carboxylic acid; grafting of organic groups onto a substrate comprising surface OH groups, by covalent bonding from organosilanes such as alkylchlorosilanes, alkylalkoxysilanes or alkylaminosilanes (cf. in particular A. Ulman, Chem. Rev., 1996, 96 , 1533-1554). In a process for grafting organic groups onto a silica substrate bearing Si-OH groups, from organotrichlorosilanes, hydrochloric acid is formed which catalyzes both the hydrolysis reaction which causes the attachment of 1 ' organosilane on the surface of the substrate, that homocondensation of the organosilanes between them. The overall process is thus accelerated at the expense of
B0437WO la sélectivité. Dans le cas des organotrichlorosilanes à courte chaîne, qui sont les silanes le plus utilisés dans des applications industrielles, les dépôts obtenus se présentent sous la forme de multicouches dont l'épaisseur est difficilement contrôlable. Lorsque l'on utilise un organotrialcoxysilane, il se forme l'alcool correspondant qui peut s ' adsorber à la surface du substrat, ce qui provoque une augmentation de l'hétérogénéité du greffage.B0437WO selectivity. In the case of short-chain organotrichlorosilanes, which are the most widely used silanes in industrial applications, the deposits obtained are in the form of multilayers whose thickness is difficult to control. When an organotrialkoxysilane is used, the corresponding alcohol is formed which can adsorb on the surface of the substrate, which causes an increase in the heterogeneity of the grafting.
Par E. Lukevics et al., (J. Organomet . Chem. 1984, 271, 307), on connaît les procédés consistant à faire réagir des organosilanes sur des composés à hydrogène mobile tels que des acides, des alcools, des thiols. Ce procédé nécessite toutefois l'utilisation d'un catalyseur, par exemple une base de Lewis, ou d'un solvant nucléophile. Par A. Fadeev, et al., (J. Am. Chem. Soc. 1999, 121, 12184), on connaît un procédé consistant à faire réagir un organosilane RSiH3, R2SiH2 ou R3SiH avec l'oxyde de titane. Par A. Ulman .et al., (Chem. Mat. 2002, 14, 1778), on connaît un procédé consistant à faire réagir 1 ' octadécyltrihydro- silane sur des particules de γ-Fe203. Les films obtenus selon ces procédés sont peu stables, parce que les réactions entraînent la formation de liaisons Si-O-M labiles (M étant selon le cas Ti ou Fe) , qui peuvent être redistribuées en Si-O-Si + M-O-M plus stables. La présente invention a pour but de fournir un procédé pour l'obtention de substrats de silice modifiés en surface par dépôt d'une couche dense homogène et bien organisée.By E. Lukevics et al., (J. Organomet. Chem. 1984, 271, 307), the methods are known which consist in reacting organosilanes on compounds with mobile hydrogen such as acids, alcohols, thiols. This process however requires the use of a catalyst, for example a Lewis base, or a nucleophilic solvent. By A. Fadeev, et al. (J. Am. Chem. Soc. 1999, 121, 12184), a process is known which consists in reacting an organosilane RSiH 3 , R 2 SiH 2 or R 3 SiH with the oxide. titanium. By A. Ulman. Et al., (Chem. Mat. 2002, 14, 1778), a process is known which consists in reacting octadecyltrihydro-silane on particles of γ-Fe 2 0 3 . The films obtained according to these methods are not very stable, because the reactions lead to the formation of labile Si-OM bonds (M being, as the case may be Ti or Fe), which can be redistributed into more stable Si-O-Si + MOM. The object of the present invention is to provide a process for obtaining surface-modified silica substrates by depositing a dense, homogeneous and well-organized layer.
Le procédé selon l'invention consiste à mettre en contact un substrat minéral portant des fonctions silanols à sa surface avec une solution d'un organotrihydrosilane dans un solvant organique, à une température inférieure à 30 °C.The process according to the invention consists in bringing a mineral substrate carrying silanol functions on its surface into contact with a solution of an organotrihydrosilane in an organic solvent, at a temperature below 30 ° C.
Comme exemple de substrat minéral portant des fonctions silanols à sa surface, on peut citer notamment des particules de silice, les plaques de verre, les plaques de quartz ou les plaques de mica, ainsi que le silicium du type wafer recouvert par une couche de silice déposée par un traitement préliminaire approprié. Un substrat de silicium du type wafer portant à sa surface une couche de silice peut être obtenu selon différents procédés. Un premier procédé consiste à enlever la couche de silice native par trempage du substrat de silicium dans une solution de HF contenant au moins 10% en volume de HF dans l'eau ultra-pure sous ultra-sons, à rincer à l'eau ultrapure, puis à traiter par l'ozone sous UV. Un tel traitement, qui est particulièrement préféré, est décrit notamment par J.R. Vig, J. Vac. Sci. Technol., 1985, 3, 1027-1034. Un deuxième procédé consiste à soumettre ledit substrat de silicium à un flux d'oxygène à température élevée, par exemple à 1150°C, tel que décrit notamment par D.L. Angst, Langmuir, 1991, 7, 2236-2242. Dans un autre procédé, le substrat de silicium est soumis à une oxydation chimique par voie basique : après nettoyage de la surface du substrat par un solvant sous ultra-sons, le substrat est laissé dans un mélange H20, NH4OH, H202 5/1/1, puis rincé à l'eau désioni- sée, séché et réhydraté (Cf. par exemple "J.D. Legrange, et al., Langmuir, 1993, 9, 1749-1753"). Dans un autre procédé, le substrat de silicium est soumis à une oxydation chimique par voie acide : le substrat est nettoyé avec une solution basique, puis plongé dans un mélange acide du type H2S04/H2θ2 (Cf. A.K. Kakkar, et al., Langmuir, 1998, 14, 6941-6947).As an example of a mineral substrate carrying silanol functions on its surface, mention may in particular be made of silica particles, glass plates, quartz plates or mica plates, as well as silicon of the wafer type covered by a layer of silica. filed by appropriate preliminary processing. A wafer-type silicon substrate carrying a layer of silica on its surface can be obtained by various methods. A first method consists in removing the native silica layer by soaking the silicon substrate in an HF solution containing at least 10% by volume of HF in ultra-pure water under ultrasound, rinsing with ultrapure water. , then treat with ozone under UV. Such treatment, which is particularly preferred, is described in particular by JR Vig, J. Vac. Sci. Technol., 1985, 3, 1027-1034. A second method consists in subjecting said silicon substrate to a flow of oxygen at a high temperature, for example at 1150 ° C., as described in particular by DL Angst, Langmuir, 1991, 7, 2236-2242. In another process, the silicon substrate is subjected to chemical oxidation by the basic route: after cleaning the surface of the substrate with a solvent under ultrasound, the substrate is left in a mixture H 2 0, NH 4 OH, H 2 0 2 5/1/1, then rinsed with deionized water, dried and rehydrated (Cf. for example "JD Legrange, et al., Langmuir, 1993, 9, 1749-1753"). In another process, the silicon substrate is subjected to an acidic chemical oxidation: the substrate is cleaned with a basic solution, then immersed in an acid mixture of the H 2 S0 4 / H 2 θ 2 type (Cf. AK Kakkar , et al., Langmuir, 1998, 14, 6941-6947).
L'étape de greffage proprement dit, c'est-à-dire la mise en contact de 1 ' organotrihydrosilane et du substrat de silice, est effectuée en atmosphère neutre (de préférence sous argon), en utilisant une solution d' organotrihydrosilane dans un solvant aprotique. Parmi les solvants aprotiques, il est préférable d'utiliser ceux qui ont un faible caractè- re hygroscopique. A titre d'exemple, on peut citer le tétrachlorure de carbone, le trichloroéthylène et le toluène.The actual grafting step, that is to say bringing the organotrihydrosilane into contact with the silica substrate, is carried out in a neutral atmosphere (preferably under argon), using an organotrihydrosilane solution in a aprotic solvent. Among the aprotic solvents, it is preferable to use those which have a low hygroscopic character. By way of example, mention may be made of carbon tetrachloride, trichlorethylene and toluene.
L' organotrihydrosilane peut être choisi parmi les composés X-E-SiH3 dans lesquels E est un segment espaceur et X représente H ou une fonction terminale réactive. X peut être choisi parmi toute fonction susceptible de permettre la fixation d'autres groupements organiques (par exemple un groupe a iné, un halogène, un époxy, un pyridyle, un ester, un tosylate (p-toluènesulfonyle) , un hétéro- cumulène (tel qu'un isocyanate, un isothiocyanate ou un carbodiimide) ou un agent complexant des métaux (par exemple un éther couronne, un cryptand, un calixarène qui est un macrocycle obtenu par condensation d'un dérivé phénolique avec le formaldéhyde) .The organotrihydrosilane can be chosen from the compounds XE-SiH 3 in which E is a spacer segment and X represents H or a reactive terminal function. X can be chosen from any function capable of allowing the attachment of other organic groups (for example an inated group, a halogen, an epoxy, a pyridyl, an ester, a tosylate (p-toluenesulfonyl), a hetero- cumulene (such as an isocyanate, isothiocyanate or carbodiimide) or a metal complexing agent (for example a crown ether, a cryptand, a calixarene which is a macrocycle obtained by condensation of a phenolic derivative with formaldehyde).
Le groupe espaceur E permet de conférer des propriétés particulières au film obtenu par la mise en œuvre du procédé. Le groupe E est choisi parmi les radicaux permettant d'obtenir une monocouche organisée. Un radical E du type alkylene à longue chaîne permet une interaction interchaînes. Parmi les radicaux E du type alkylene, on préfère tout particulièrement ceux qui ont de 8 à 24 atomes de carbone. Un radical E comprenant deux triples liaisons -C≡C- permet une réticulation. Un radical E comprenant une chaîne aromatique conjuguée confère des propriétés d'optique non linéaire. A titre d'exemple, on peut citer les radicaux phénylène-vinylène et phénylène-acétylène . Un radical E du type pyrrole, thiophène ou polysilane confère une conduction, électronique. Un radical E du type polyaromatique hétéro- substitué confère des propriétés de photo/ électroluminescence. A titre d'exemple, on peut citer les quinones et les composés diazoïques. Un groupe E du type alkyle ou fluoro- alkyle, en particulier un groupe alkyle ou fluoroalkyle ayant de 3 à 24 atomes de carbone, permet d'utiliser les couches obtenues en chromatographie ou en électrophorèse.The spacer group E makes it possible to confer particular properties on the film obtained by implementing the method. Group E is chosen from the radicals making it possible to obtain an organized monolayer. A long chain alkylene type E radical allows interchain interaction. Among the radicals E of the alkylene type, very particularly preferred are those which have from 8 to 24 carbon atoms. A radical E comprising two triple bonds -C≡C- allows crosslinking. A radical E comprising a conjugated aromatic chain confers non-linear optical properties. By way of example, mention may be made of the phenylene-vinylene and phenylene-acetylene radicals. A radical E of the pyrrole, thiophene or polysilane type confers electronic conduction. A radical E of the heterosubstituted polyaromatic type confers photo / electroluminescence properties. By way of example, mention may be made of quinones and diazo compounds. A group E of the alkyl or fluoroalkyl type, in particular an alkyl or fluoroalkyl group having from 3 to 24 carbon atoms, makes it possible to use the layers obtained in chromatography or in electrophoresis.
La solution d' organotrihydrosilane contient de préférence de 10~3 à 10"1 mole/1. Des solutions dans lesquelles la concentration en organotrihydroxilane est de l'ordre de 10-2 mole/1 sont particulièrement préférées. La durée du greffage est de préférence comprise entre 4 et 24 heures. Une durée l'ordre de 12 h permet d'obtenir de bons résultats.The organotrihydrosilane solution preferably contains from 10 ~ 3 to 10 "1 mole / 1. Solutions in which the concentration of organotrihydroxilane is of the order of 10 -2 mole / 1 are particularly preferred. The duration of the grafting is preferably between 4 and 24 hours, a duration of around 12 hours allows good results to be obtained.
Pendant le greffage, le milieu réactionnel doit être maintenu à une température inférieure à 30 °C. La valeur limite dépend du substituant X-E-. Cette valeur limite a tendance à diminuer lorsque le nombre d'atomes de carbone du substituant diminue. La détermination de la valeur limite pour un substituant donné est à la portée de l'homme de métier. Des informations utiles peuvent être trouvées notamment dans Brzoska et al, (Langmuir, 1994, 10, 4367), qui mentionne l'existence d'une température critique Te contrôlant la qualité des monocouches auto-assemblées obtenues à partir de différents alkyltrichlorosilanes. La température limite est généralement inférieure à 30 °C. Par exemple, la température doit être inférieure à 30°C si R est CιsH37 et inférieure à 10 °C si R est Cι2H25.During the grafting, the reaction medium must be maintained at a temperature below 30 ° C. The limit value depends on the substituent XE-. This limit value tends to decrease when the number of carbon atoms of the substituent decreases. The determination of the limit value for a given substituent is within the reach of the man of job. Useful information can be found in particular in Brzoska et al, (Langmuir, 1994, 10, 4367), which mentions the existence of a critical temperature Te controlling the quality of the self-assembled monolayers obtained from different alkyltrichlorosilanes. The limit temperature is generally less than 30 ° C. For example, the temperature must be less than 30 ° C if R is CιsH 37 and less than 10 ° C if R is Cι 2 H 25 .
Il est préférable d'effectuer la réaction • sous atmosphère inerte, afin d'éviter la pollution de la monocouche par des composés organiques.It is preferable to conduct the reaction under an inert atmosphere • in order to avoid pollution of the monolayer by organic compounds.
L'utilisation d'un organosilane X-E-SiH3 comme agent de couplage permet la formation initiale d'une liaison Si-O-Si par condensation directe entre la fonction Si-H du réactif avec une fonction silanol Si-OH portée par la surface du substrat. Ce mode de greffage limite considérablement la formation d'agrégats, préjudiciables au dépôt d'une couche homogène. L'utilisation de X-E-SiH3 présente en outre l'avantage de produire des sous-produits faciles à éliminer, à savoir H2. Il n'y a aucun risque de trouver sur le substrat traité, des entités anioniques ou des composés protiques inhérents aux procédés de l'art antérieur utilisant les chlorosilanes ou les alcoxysilanes .The use of an organosilane XE-SiH 3 as a coupling agent allows the initial formation of an Si-O-Si bond by direct condensation between the Si-H function of the reagent with a Si-OH silanol function carried by the surface. of the substrate. This grafting method considerably limits the formation of aggregates, which are detrimental to the deposition of a homogeneous layer. The use of XE-SiH 3 also has the advantage of producing easily eliminated by-products, namely H 2 . There is no risk of finding anionic entities or protic compounds inherent in the processes of the prior art using chlorosilanes or alkoxysilanes on the treated substrate.
Il faut noter également que le procédé proposé peut être mis en œuvre sans intervention d'un catalyseur, contrairement aux procédés de l'art antérieur consistant à faire réagir des organosilanes sur des composés à hydrogène mobile tels que des acides, des alcools, des thiols (Cf. E. Lukevics et al., précité). Le substrat de silice modifié selon le procédé de la présente invention comporte à sa surface une monocouche de segments X-E- fixés par liaison covalente Si-O-Si, ladite couche comportant des fonctions X uniformément réparties sur la surface et accessibles. Le procédé de l'invention consiste à déposer une monocouche organique sur une couche de surface de silice initialement très hydrophile, l'angle de contact étant inférieur à 10°. Après le greffage, la mouillabilité de la oIt should also be noted that the proposed process can be implemented without the intervention of a catalyst, unlike the processes of the prior art consisting in reacting organosilanes on compounds with mobile hydrogen such as acids, alcohols, thiols (See E. Lukevics et al., Cited above). The silica substrate modified according to the method of the present invention comprises on its surface a monolayer of XE- segments fixed by covalent Si-O-Si bond, said layer comprising X functions uniformly distributed over the surface and accessible. The method of the invention consists in depositing an organic monolayer on a surface layer of initially very hydrophilic silica, the contact angle being less than 10 °. After grafting, the wettability of the o
surface vis-à-vis de l'eau ultra-pure dépend fortement de la nature des groupements X-E- du silane utilisé pour former la couche. Dans le cas d' alkylsilanes (E étant un alkylene linéaire) le caractère hydrophobe de la surface se traduit par un angle de contact θH2o ≈ 95-100°. Lorsque E est un aryle, la présence de groupements aromatiques diminue le caractère hydrophobe de la surface, ce qui se traduit par un angle de contact θH2o ≈ 69-77°. La figure 1 illustre l'état d'une goutte d'eau sur une surface hydrophile, l'angle θ étant inférieur à 90°. La figure 2 illustre l'état d'une goutte d'eau sur une surface hydrophobe, l'angle θ étant supérieur à 90° .surface vis-à-vis ultra-pure water strongly depends on the nature of the XE- groups of the silane used to form the layer. In the case of alkylsilanes (E being a linear alkylene) the hydrophobic character of the surface results in a contact angle θ H 2o ≈ 95-100 °. When E is an aryl, the presence of aromatic groups reduces the hydrophobic nature of the surface, which results in a contact angle θ H2 o ≈ 69-77 °. FIG. 1 illustrates the state of a drop of water on a hydrophilic surface, the angle θ being less than 90 °. FIG. 2 illustrates the state of a drop of water on a hydrophobic surface, the angle θ being greater than 90 °.
Les images obtenues par AFM (microscopie de force atomique) montrent que la surface est homogène et présente une très faible rugosité moyenne de surface (RMS) , généralement inférieure à 0,2 nm. La rugosité du substrat traité est indépendante de la nature du groupement organique greffé, elle reste très proche de celle du substrat initial non traité.The images obtained by AFM (atomic force microscopy) show that the surface is homogeneous and has a very low average surface roughness (RMS), generally less than 0.2 nm. The roughness of the treated substrate is independent of the nature of the grafted organic group, it remains very close to that of the initial untreated substrate.
L'épaisseur de la couche obtenue est déterminée par ellipsométrie, (en prenant n=l,45 pour valeur d'indice de réfraction du film de surface, qui est la valeur généralement utilisée) . Cette épaisseur dépend de la longueur du groupe X-E- et de son orientation par rapport à la surface du substrat. L'épaisseur est de l'ordre de 1,7 nm lorsque X-E- est 1 ' octadécyle, ce qui correspond à une couche dispersée occupant s 70% de la surface du substrat.The thickness of the layer obtained is determined by ellipsometry, (taking n = 1.45 for the refractive index value of the surface film, which is the value generally used). This thickness depends on the length of the X-E- group and its orientation relative to the surface of the substrate. The thickness is of the order of 1.7 nm when X-E- is 1 octadecyl, which corresponds to a dispersed layer occupying 70% of the surface of the substrate.
Le substrat revêtu d'une monocouche obtenue par le procédé proposé se caractérise de manière générale par un bon taux de recouvrement et une bonne organisation des chaînes à sa surface.The substrate coated with a monolayer obtained by the proposed process is generally characterized by a good recovery rate and a good organization of the chains on its surface.
Dans un substrat modifié à partir d'un silane du type alkyl-SiH3, la liaison covalente par laquelle le substrat est fixé au groupe organique est du type -SiH20-Si-. La présence de groupes SiH2 est révélée par la bande de vibration si-H à 2150 cm-1. Cette bande ne se constate pas sur les substrats modifiés selon les procédés de l'art antérieur à l'aide d'un alkyltrichlorosilane ou d'un alkyltrialcoxysilane comprenant le même groupe alkyle. La présente invention est décrite plus en détail à l'aide des exemples suivants, auxquels elle n'est cependant pas limitée.In a substrate modified from a silane of the alkyl-SiH 3 type , the covalent bond by which the substrate is attached to the organic group is of the -SiH 2 O-Si- type. The presence of SiH 2 groups is revealed by the si-H vibration band at 2150 cm -1 . This band is not found on the substrates modified according to the methods of the prior art using an alkyltrichlorosilane or an alkyltrialkoxysilane comprising the same alkyl group. The present invention is described in more detail with the aid of the following examples, to which it is not however limited.
Exemple 1 On a préparé une série de substrats de silicium revêtus d'une couche organique par traitement avec l'octadécyl- trihydrosilane .Example 1 A series of silicon substrates coated with an organic layer were prepared by treatment with octadecyl trihydrosilane.
Comme substrat, on a utilisé des disques de silicium (1,0,0) taillés pour obtenir des plaquettes rectangulaires de 1 x 2 cm2.As substrate, cut silicon disks (1,0,0) were used to obtain rectangular plates of 1 x 2 cm 2 .
Dans une première étape, chaque plaquette a été trempée dans une solution de HF concentré pendant quelques secondes, jusqu'à ce que la surface soit devenue totalement hydrophobe. Ensuite, chaque plaquette a été rincée à l'eau ultra-pure, puis traitée par l'ozone sous UV.In a first step, each wafer was soaked in a concentrated HF solution for a few seconds, until the surface became completely hydrophobic. Then, each plate was rinsed with ultra-pure water, then treated with ozone under UV.
Chaque plaquette ainsi traitée a immédiatement été introduite dans un tube de Schlenck contenant 20 ml d'une solution 10~2 M d'octadécyltrihydrosilane dans du CC14, et maintenue dans le tube pendant 24 h à une température de 15°C, sans agitation. Après 24 h, les plaquettes ont été extraites des tubes de Schlenck, lavées au CC14, à 1 ' éthanol absolu, puis au chloroforme, chaque lavage étant effectué sous ultrasons, pendant une durée de l'ordre de 5 min.Each plate thus treated was immediately introduced into a Schlenck tube containing 20 ml of a 10 ~ 2 M solution of octadecyltrihydrosilane in CC1 4 , and kept in the tube for 24 h at a temperature of 15 ° C, without shaking. . After 24 h, the platelets were extracted from the Schlenck tubes, washed with CCl 4 , with absolute ethanol, then with chloroform, each washing being carried out under ultrasound, for a period of the order of 5 min.
Les plaquettes ainsi obtenues peuvent être conservées sous atmosphère ambiante, sans subir de dégradation.The platelets thus obtained can be stored in an ambient atmosphere, without undergoing degradation.
L'angle de contact à la surface des plaquettes, mesuré par la méthode de la goutte à l'équilibre, est de 98° ± 2, ce qui témoigne d'une surface hydrophobe et homogène.The contact angle on the surface of the platelets, measured by the equilibrium drop method, is 98 ° ± 2, which indicates a hydrophobic and homogeneous surface.
Dans les mêmes conditions que ci-dessus, on a traité des plaquettes de silicium à l'aide d' octadécyltrichlorosilane, à titre comparatif.Under the same conditions as above, silicon wafers were treated with octadecyltrichlorosilane, for comparison.
Une analyse par spectroscopie infrarouge en mode de réflexion totale atténuée (ATR) des surfaces traitées parAn analysis by infrared spectroscopy in attenuated total reflection mode (ATR) of the surfaces treated with
1 ' octadécyltrihydrosilane et des surfaces traitées par 1 Octadécyltrichlorosilane a donné les résultats regroupés dans le tableau suivant. 1 octadecyltrihydrosilane and surfaces treated with 1 Octadecyltrichlorosilane gave the results grouped in the following table.
Les substrats traités selon l'invention présentent une bande Vsi-H à 2150 cm"1 qui n'existe pas pour les substrats obtenus à partir de Cι8H37SiCl3 et qui correspond à l'existence de liaisons Si-H dans un environnement du typeThe substrates treated according to the invention have a Vsi-H band at 2150 cm "1 which does not exist for the substrates obtained from Cι 8 H 37 SiCl 3 and which corresponds to the existence of Si-H bonds in a type environment
R-SiH2-0 à la surface du substrat.R-SiH 2 -0 on the surface of the substrate.
Les autres bandes obtenues montrent que l'organisation de 1 ' octadécyltrihydrosilane en surface est un compromis entre une réticulation complète obtenue pour l'octadécyl- trichlorosilane greffé et l'absence d'organisation observée pour 1 ' octadécyltrihydrosilane et p.our 1 ' octadécyltrichlorosilane en solution.The other bands obtained show that the organization of octadecyltrihydrosilane on the surface is a compromise between a complete crosslinking obtained for the grafted octadecyltrichlorosilane and the absence of organization observed for octadecyltrihydrosilane and for octadecyltrichlorosilane in solution.
Les images obtenues en AFM pour les plaquettes de l'invention montrent une surface homogène avec une très faible rugosité, de l'ordre de 0,15 - 0,20 nm.The images obtained in AFM for the wafers of the invention show a homogeneous surface with a very low roughness, of the order of 0.15 - 0.20 nm.
L'épaisseur des couches obtenues selon le procédé de l'invention a été déterminée par ellipsométrie, en prenant n=l,45 pour valeur d'indice de réfraction. Cette épaisseur est de l'ordre de 1,7 nm, ce qui correspond à une couche dispersée occupant = 70% de la surface du substrat.The thickness of the layers obtained according to the process of the invention was determined by ellipsometry, taking n = 1.45 for the refractive index value. This thickness is of the order of 1.7 nm, which corresponds to a dispersed layer occupying = 70% of the surface of the substrate.
Exemple 2Example 2
On a reproduit le mode opératoire de l'exemple 1 en utilisant 1 ' octadécyltrihydrosilane, en changeant uniquement la température de réaction dans le tube de Schlenck. Deux séries d'essais ont été effectuées respectivement à 5°C et à 20°C. Les analyses effectuées sur les plaquettes ont donné des résultats identiques. Exemple 3The procedure of Example 1 was reproduced using octadecyltrihydrosilane, only changing the reaction temperature in the Schlenck tube. Two series of tests were carried out at 5 ° C and 20 ° C respectively. The analyzes carried out on the platelets gave identical results. Example 3
On a reproduit le mode opératoire de l'exemple 1, mais en remplaçant 1 ' octadécytrihydrosilane par le phényltri- hydrosilane, toutes les autres conditions étant identiques. L'angle de contact mesuré sur la surface des plaquettes modifiées est de 74°±4.The procedure of Example 1 was reproduced, but replacing the octadecytrihydrosilane with phenyltrihydrosilane, all the other conditions being identical. The contact angle measured on the surface of the modified inserts is 74 ° ± 4.
Les images obtenues en AFM pour les plaquettes de 1 ' invention montrent une surface homogène avec une très faible rugosité, de l'ordre de 0,2 nm. L'épaisseur des couches obtenues selon le procédé de l'invention a été déterminée par ellipsométrie, en prenant n=l,45 pour valeur d'indice de réfraction. Cette épaisseur est de l'ordre de 0,8 nm, ce qui correspond à une monocouche de densité élevée.The images obtained in AFM for the wafers of the invention show a homogeneous surface with a very low roughness, of the order of 0.2 nm. The thickness of the layers obtained according to the process of the invention was determined by ellipsometry, taking n = 1.45 for the refractive index value. This thickness is of the order of 0.8 nm, which corresponds to a high density monolayer.
Exemple 4Example 4
On a traité une série de plaquettes selon le mode opératoire de l'exemple 1, mais en remplaçant l' octadécyltrihydrosilane par le p-méthylstilbényl trihydrosilane, toutes les autres conditions étant identiques. La figure 3 illustre l'état de surface de la plaquette après greffage du p-méthylstilbényltrihydrosilane .A series of platelets was treated according to the procedure of Example 1, but replacing the octadecyltrihydrosilane with p-methylstilbényl trihydrosilane, all the other conditions being identical. FIG. 3 illustrates the surface condition of the wafer after grafting of p-methylstilbényltrihydrosilane.
L'angle de contact mesuré sur la surface des plaquettes modifiées est de 85°+ 3.The contact angle measured on the surface of the modified inserts is 85 ° + 3.
Les images obtenues en AFM pour les plaquettes montrent une surface homogène avec une très faible rugosité, de l'ordre de 0,2 nm.The images obtained in AFM for the platelets show a homogeneous surface with a very low roughness, of the order of 0.2 nm.
L'épaisseur des couches obtenues a été déterminée par ellipsométrie, en prenant n=l,619 pour valeur d'indice de réfraction. Cette épaisseur est de l'ordre de 19 nm, ce qui correspond à une monocouche de densité élevée.The thickness of the layers obtained was determined by ellipsometry, taking n = 1.619 as the refractive index value. This thickness is of the order of 19 nm, which corresponds to a high density monolayer.
Exemple 5Example 5
On a traité une série de plaquettes selon le mode opératoire de l'exemple 1, mais en remplaçant l' octadécyltrihydrosilane par le vinylphényl trihydrosilane, toutes les autres conditions étant identiques.A series of platelets was treated according to the procedure of Example 1, but replacing the octadecyltrihydrosilane with vinylphenyl trihydrosilane, all the other conditions being identical.
L'angle de contact mesuré sur la surface des plaquettes modifiées est de 75°+ 4. Les images obtenues en AFM pour les plaquettes montrent une surface homogène avec une très faible rugosité, de l'ordre de 0,2 nm.The contact angle measured on the surface of the modified wafers is 75 ° + 4. The images obtained in AFM for the platelets show a homogeneous surface with a very low roughness, of the order of 0.2 nm.
L'épaisseur des couches obtenues a été déterminée par ellipsométrie, en prenant n=l,546 pour valeur d'indice de réfraction. Cette épaisseur est de l'ordre de 11 nm, ce qui correspond à une monocouche de densité élevée.The thickness of the layers obtained was determined by ellipsometry, taking n = 1.546 for the refractive index value. This thickness is of the order of 11 nm, which corresponds to a high density monolayer.
Chaque plaquette ainsi traitée a été placée dans un ballon de 25 ml surmonté d'un réfrigérant et contenant 1 mmole de p-bromotoluène, 9 mg (0,04 mmole) de diacétate de palladium, 46 mg (0,15 mmole) de triorthotolylphosphine,Each plate thus treated was placed in a 25 ml flask surmounted by a condenser and containing 1 mmol of p-bromotoluene, 9 mg (0.04 mmol) of palladium diacetate, 46 mg (0.15 mmol) of triorthotolylphosphine ,
2 ml de triéthylamine et 10 ml de toluène, le tout sous atmosphère inerte. Le mélange réactionnel a été porté à2 ml of triethylamine and 10 ml of toluene, all under an inert atmosphere. The reaction mixture was brought to
110 °C sous faible agitation magnétique pendant une nuit. Après retour à température ambiante, chaque plaquette a été sortie du ballon, puis soigneusement rincée au toluène et au pentane sous ultrasons. La figure 4 illustre l'état de surface de la plaquette après réaction post-greffage du p- bromotoluène . Les plaquettes ainsi obtenues peuvent être conservées sous atmosphère ambiante, sans subir de dégradation.110 ° C with weak magnetic stirring overnight. After returning to ambient temperature, each plate was removed from the flask, then carefully rinsed with toluene and pentane under ultrasound. FIG. 4 illustrates the surface condition of the wafer after the post-grafting reaction of p-bromotoluene. The platelets thus obtained can be stored in an ambient atmosphere, without undergoing degradation.
Les analyses effectuées sur les plaquettes ont donné des résultats identiques à ceux obtenus pour les analyses des plaquettes traitées dans l'exemple 4.The analyzes carried out on the platelets gave results identical to those obtained for the analyzes of the platelets treated in Example 4.
Exemple 6Example 6
Le procédé selon 1 ' invention a été mis en œuvre pour un substrat de silice sous forme de silice colloïdale.The method according to the invention has been implemented for a silica substrate in the form of colloidal silica.
Le substrat est une silice activée commercialisée par la société Merck sous la dénomination Silice Merck 60F. On a traité 0,5 g de la silice activée par 1 g d' octadécyltrihydrosilane dans 20 ml de CC14 à 19-20 °C pendant 24 h sous agitation magnétique. La poudre obtenue a été filtrée, lavée 2 fois avec 20 ml de CC14, puis 4 fois avec 20 ml de THF pour éliminer les éventuels silanes physisorbés.The substrate is an activated silica sold by the company Merck under the name Silica Merck 60F. 0.5 g of the activated silica was treated with 1 g of octadecyltrihydrosilane in 20 ml of CCl 4 at 19-20 ° C for 24 h with magnetic stirring. The powder obtained was filtered, washed 2 times with 20 ml of CC1 4 , then 4 times with 20 ml of THF to remove any physisorbed silanes.
On constate que des grains de la poudre obtenue, déposés sur une surface d'eau ultrapure, restent en surface après 48 heures, ce qui démontre un caractère parfaitement hydrophobe.It is noted that grains of the powder obtained, deposited on a surface of ultrapure water, remain on the surface after 48 hours, which demonstrates a perfectly hydrophobic character.
La présence de silane greffé est caractérisée par spectroscopie infrarouge et RMN. Une bande IR à 2165 cm"1 et un signal à -31 ppm en RMN 29Si montrent la présence de fonctions -0-SiR (H) -0- . Ce résultat suppose l'hydrolyse d'une liaison Si-H, consécutive à la fixation de 1 'organosilane sur la surface. The presence of grafted silane is characterized by infrared and NMR spectroscopy. An IR band at 2165 cm −1 and a signal at -31 ppm in NMR 29 Si show the presence of -0-SiR (H) -0- functions. This result supposes the hydrolysis of a consecutive Si-H bond fixing the organosilane on the surface.

Claims

Revendications claims
1. Procédé pour l'obtention d'un substrat minéral modifié en surface par une couche organique, caractérisé en ce qu'il consiste à mettre en contact un substrat minéral portant des fonctions silanols à sa surface, avec une solu- tion d'un organotrihydrosilane dans un solvant organique, à une température inférieure à 30°C.1. A method for obtaining a mineral substrate modified at the surface by an organic layer, characterized in that it consists in bringing a mineral substrate carrying silanol functions onto its surface, with a solution of organotrihydrosilane in an organic solvent, at a temperature below 30 ° C.
2. Procédé selon la revendication 1, caractérisé en ce que le substrat minéral portant des fonctions silanols à sa surface est un substrat constitué par de la silice. 2. Method according to claim 1, characterized in that the mineral substrate carrying silanol functions on its surface is a substrate constituted by silica.
3. Procédé selon la revendication 1, caractérisé en ce que le substrat minéral portant des fonctions silanols à sa surface est un substrat de silicium portant à sa surface une couche de silice.3. Method according to claim 1, characterized in that the mineral substrate carrying silanol functions on its surface is a silicon substrate carrying on its surface a layer of silica.
4. Procédé selon la revendication 1, caractérisé en ce que le substrat minéral portant des fonctions silanols à sa surface est une plaque de verre, de mica ou de quartz.4. Method according to claim 1, characterized in that the mineral substrate carrying silanol functions on its surface is a plate of glass, mica or quartz.
5. Procédé selon la revendication 1, caractérisé en ce que la réaction est effectuée en atmosphère neutre.5. Method according to claim 1, characterized in that the reaction is carried out in a neutral atmosphere.
6. Procédé selon la revendication 1, caractérisé en ce que le solvant est un solvant aprotique.6. Method according to claim 1, characterized in that the solvent is an aprotic solvent.
7. Procédé selon la revendication 6, caractérisé en ce que le solvant est choisi le tétrachlorure de carbone, le trichloroéthylène et le toluène.7. Method according to claim 6, characterized in that the solvent is chosen carbon tetrachloride, trichlorethylene and toluene.
8. Procédé selon la revendication 1, caractérisé en ce que 1 ' organotrihydrosilane répond à la formule X-E-SiH3 dans laquelle E est un segment espaceur et X représente H ou une fonction terminale réactive.8. Process according to claim 1, characterized in that the organotrihydrosilane corresponds to the formula XE-SiH 3 in which E is a spacer segment and X represents H or a reactive terminal function.
9. Procédé selon la revendication 8, caractérisé en ce que X représente un groupe amino, un halogène, un époxy, un pyridyle, un ester, un tosylate ou un hétérocumulène .9. Method according to claim 8, characterized in that X represents an amino group, a halogen, an epoxy, a pyridyl, an ester, a tosylate or a heterocumulene.
10. Procédé selon la revendication 8, caractérisé en ce que X représente un agent complexant des métaux10. Method according to claim 8, characterized in that X represents a metal complexing agent
11. Procédé selon la revendication 10, caractérisé en ce que X est un éther couronne, un cryptand ou un calixarène. 11. Method according to claim 10, characterized in that X is a crown ether, a cryptand or a calixarene.
12. Procédé selon la revendication 8, caractérisé en ce que le groupe espaceur E est un radical alkylene à longue chaîne.12. The method of claim 8, characterized in that the spacer group E is a long chain alkylene radical.
13. Procédé selon la revendication 8, caractérisé en ce que le groupe espaceur E est radical hydrocarboné comprenant deux triples liaisons -G≡C-.13. The method of claim 8, characterized in that the spacer group E is a hydrocarbon radical comprising two triple bonds -G≡C-.
14. Procédé selon la revendication 8, caractérisé en ce que le groupe espaceur E comprend une chaîne aromatique conjuguée . 14. Method according to claim 8, characterized in that the spacer group E comprises a conjugated aromatic chain.
15. Procédé selon la revendication 8, caractérisé en ce que le groupe espaceur E est un pyrrole, ou thiophène .15. The method of claim 8, characterized in that the spacer group E is a pyrrole, or thiophene.
16. Procédé selon la revendication 1, caractérisé en ce que la solution d' organotrihydrosilane contient de 0,001 à 0,1 mole /l. 16. Method according to claim 1, characterized in that the organotrihydrosilane solution contains from 0.001 to 0.1 mol / l.
17. Procédé selon la revendication 1, caractérisé en ce que la durée du greffage est comprise entre 4 et 24 heures .17. Method according to claim 1, characterized in that the duration of the grafting is between 4 and 24 hours.
18. Substrat minéral revêtu par une monocouche organique, obtenu par le procédé selon l'une des revendications 1 à 17.18. Inorganic substrate coated with an organic monolayer, obtained by the process according to one of claims 1 to 17.
19. Substrat minéral revêtu par une monocouche organique obtenu par le procédé selon la revendication 12, caractérisé en ce que la monocouche est constituée de radicaux alkylènes fixés par des liaisons -Si-H20-Si- dont les groupes SiH2 sont caractérisés par une bande de vibration si-H à 2150 cm"1. 19. Inorganic substrate coated with an organic monolayer obtained by the process according to claim 12, characterized in that the monolayer consists of alkylene radicals attached by -Si-H 2 0-Si- bonds whose SiH 2 groups are characterized by a vibration band si-H at 2150 cm "1 .
EP03755999A 2002-05-31 2003-05-20 Method for the production of a mineral substrate with modified surface and substrate thus obtained Withdrawn EP1509480A1 (en)

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FR0206736A FR2840297B1 (en) 2002-05-31 2002-05-31 PROCESS FOR PRODUCING SURFACE-MODIFIED MINERAL SUBSTRATE, AND SUBSTRATE OBTAINED
FR0206736 2002-05-31
PCT/FR2003/001515 WO2003101905A1 (en) 2002-05-31 2003-05-20 Method for the production of a mineral substrate with modified surface and substrate thus obtained

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US20050214546A1 (en) 2005-09-29
WO2003101905A1 (en) 2003-12-11
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FR2840297B1 (en) 2005-03-25
JP2005528262A (en) 2005-09-22

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