WO2000000559A1

WO2000000559A1 - Crosslinkable silicone composition useful, in particular for producing water-repellent and/or oil-repellent coating and/or impregnation, with low surface energy

Info

Publication number: WO2000000559A1
Application number: PCT/FR1999/001516
Authority: WO
Inventors: Gérard Mignani; Philippe Olier; Christian Priou
Original assignee: Rhodia Chimie
Priority date: 1998-06-30
Filing date: 1999-06-24
Publication date: 2000-01-06
Also published as: AU4271499A; CN1310749A; CA2335926A1; FR2780407A1; JP2002519470A; EP1093497A1; BR9912505A; TR200100347T2; FR2780407B1

Abstract

The invention concerns an improved perfluorinated silicone composition to obtain antifouling coating and/or impregnation provided with improved properties for adhering to substrates and with increased life span. The invention concerns a crosslinkable silicone composition useful for making various supports water-repellent and/or oil-repellent to provide them with low surface energy. Said composition comprises: at least a POS A perfluorinated by radicals selected among the carboxylic diacid perfluorinated esters capable of forming anhydrides (e.g. maleic acid- bifid graft Gf); at least a crosslinking agent B (divinyltetramethyldisiloxane) perfluorinated or not and capable of reacting with the POS A; optionally a catalyst C; optionally one or several functional additives D. The selected crosslinking system is, for example, of the SiH/Sivinyl or the COOR/oxazolidine type with R = H, alkyl, NH4?+ of Na+¿. The invention also concerns the method for producing water-repellent and/or oil-repellent coating and/or impregnation on a support, method which consists in using said A, B, C, D composition. The invention is applicable to waterproof antifouling and/or spot-repellent coating for various bases such as textiles.

Description

CROSSLINKABLE SILICONE COMPOSITION FOR USE, IN PARTICULAR FOR PRODUCING HYDROPHOBIC AND / OR OLEOPHOBIC COATINGS AND / OR IMPREGNATIONS, WITH LOW SURFACE ENERGY

TECHNICAL AREA :

The field of the invention is that of formulations for treating supports in order to give them resistance to aqueous and fatty substances. More particularly, the invention relates to silicone compositions containing perhalogenated - preferably perfluorinated - radicals which can be used in particular for the production of hydrophobic and / or oleophobic coatings and / or impregnations, of various supports.

More particularly still, the invention relates to crosslinkable silicone compositions, capable of being used as fluorinated finishes, in the textile field to provide the treated fabrics with waterproofing, and anti-stain and / or anti-fouling properties, combined with a easy to wash.

Such properties are also advantageous for fields other than the textile field. We can cite, for example, the field of building in which coatings, paints, coatings or other water and oil repellents are used and offering resistance of non-adhesive surfaces to ice, biological soiling type of those attaching to boat hulls ("fouling"), graphitis or vis-à-vis other undesirable contaminants.

ANTERJECTOR ART:

The silicone oils grafted with fluorinated units can also be used as a lubricant, as a specific anti-adherent agent with respect to certain adhesives (silicones with high adhesive power), as an anti-greasy agent, or even as an anti- foam. They can also be formulated with different thickeners to form sealants or any other sealing and / or jointing materials. In crosslinked form, these fluorinated silicones can be formed into various technical parts by molding or by extrusion.

The present invention relates to crosslinkable silicone compositions comprising linear or cyclic perhalogenated, preferably perfluorinated, polyorganosiloxanes, having at least one silicon atom substituted by at least one perfluorinated radical Rf. The present invention also relates to this water-repellent and oil-repellent perfluorinated silicone composition, in crosslinked form.

Is also envisaged in the context of the invention, a process for producing a hydrophobic and / or oleophobic coating and / or impregnation, using said composition.

Finally, the invention relates to precursors of coatings, coatings, paints or other varnishes comprising this composition.

The role of halogens and in particular fluorine and the carbon / fluorine bond in providing specific properties to organic polymer systems, is a well-known concept in polymer chemistry. It is known in particular that fluorination, and more precisely the introduction of perfluorinated units into polymers, brings about a reduction in surface energies, an improvement in thermal and chemical stability as well as hydrophobicity, organophobia and d 'oleophobia. It is thus known that in order to resist aqueous and fatty substances, a coating must have a high density of perfluorinated end groups Rf at the surface. Since the 1970s, this type of functionalization by perfluorination has been applied to silicone polymers, in particular of the linear or cyclic polyorganosiloxane (POS) type; preferably linear.

For more details on these fluorinated silicones, one can refer to the article by OGDEN R. PffiRCE entitled "Fluorosilicons" - 1970 - John Wiley & Sons Inc. pages 1 to 15.

A first known strategy of industrial synthesis of silicones with perfluorinated units, essentially consists in "hydrosilylating" a dihalohydrogénoorganosilane, such as MeHSiCl2 (Me = methyl), by an unsaturated compound carrying a perfluorinated unit and of general formula: CHj ⁼ CH - Rf (Rf = perfluorinated motif). The addition of silane to this olefin leads to a perfluorinated dihalogenoorganosilane, which can be hydrolyzed so as to produce a functionalized silicone, which can be, for example, a cyclic tetramer. It is possible to subject the latter to a redistribution in order to obtain a linear perfluorinated polyorganosiloxane (POS). The hydrosilylation reactions which are involved in this kind of synthesis and which use various combinations of silicone hybrids and perfluorinated olefins are known to be catalyzed by selected metal compounds and in particular certain metals from group VIII such as platinum. Pt / Sn complexes have thus been used as a hydrosilylation catalyst - see US Patent No. 4,089,882 (SHINETSU). This synthesis strategy appears to be relatively complex and therefore costly. For the sake of industrial simplification, a second synthesis strategy has been proposed based on the direct hydrosilylation of a silicone with SiH motif using α-fluorinated olefin eg of the CH ^ ⁼⁼ Α - Rf type, this perfluorinated unit Rf being attached directly to the olefinic CH by a carbon atom carrying at least one fluorine atom. Again, various metal catalysts from the VTII group, in particular based on platinum, are used in the context of this hydrosilylation reaction. However, it turned out that these catalysts did not allow very high yields to be achieved. In particular, the conventional industrial hydrosilylation catalysts based on platinum (for example of the KARSTEDT type) are not very effective. In addition, it has been found that large quantities of by-product are generated, and this, obviously, to the detriment of the perfluorination of the silicones.

In US Patent No. 5,233,071, these are the ball joints that are used. They come from the hydrosilylation of α-olefins. But to overcome the shortcomings of the hydrosilylation catalysts used previously, the process described in this patent uses organometallic complexes based on cobalt [(Cθ2COg, C02 O) (PR3) 3 with R = alkyl, aryl]. Such a technical proposal appeared to be unsatisfactory, since the reaction times obtained are of the order of a few days and it is essential to use a large amount of catalyst (1-2%), which is particularly penalizing the economy of the process.

A non-negligible drawback of these cobalt-based complexes is that they catalyze reactions other than hydrosilylation. In particular, they can participate in polymerization processes by breaking of epoxy rings. This lack of specificity is particularly troublesome. In addition, these catalysts are not industrial.

US Patent No. 5,348,769 discloses linear or cyclic polyorganosiloxanes, comprising siloxy units D substituted by a first perfluorinated functional unit of formula -R- ZRf as well as other siloxy units D, carrying a second type of unit functional of the etherhydroxyl or alkylhydroxyl type. The patella or the bridge connecting Si to Rf of the first perfluorinated functional motif, is constituted in particular by: (CH2) _X Z with x = 2,3 or 4 and Z = NHCO, NHSO ₂ , O ₂ C, O ₃ S, OCH ₂ CH ₃ , NHCH ₂ CH ₂ or CH ₂ CHOHCH ₂ . The catalyst used is preferably chloroplatinic acid. Such a technique is not very simple, because it requires the prior preparation of the olefinic reagent perfluoroalkylated. This significantly lengthens the synthesis times and consequently it increases the cost price of the process.

Apart from these ball joints whose precursors are perfluoroalkylated α-olefins of formula CH2 = CH - Rf, the prior technical literature also describes bridges whose olefinic precursors are of the CH2 = CH- () -Rf type; the chemical bond between (E) and Rf being an ester bond. The latter results from the reaction of a carboxylic function with a perhalogenated alcohol, preferably perfluorinated. And generally, said carboxylic function is the product of the hydrolysis of an acid anhydride. Thus, PCT patent application WO 94/12561 discloses POS grafted with fluorinated units only in the α and ω position at the ends of the silicone chains. These POS -ω alkyl esterfluorinated do not have optimal properties with regard to the lowering of surface tension as well as oleophobia and hydrophobia. European patent application No. 0 640 644 describes, for its part, perfluorinated silicone derivatives (Rf), which can be used in cosmetic formulations. These perfluorinated silicone derivatives are characterized by D siloxyl units, carrying perfluorinated grafts of three different types, namely:

CH. ^O - CH,) - Rf - (CH,) - (OR - 0— (CH ^ Rf

W ( ² ) (CH,), - O CH _j

I

CH O- X— R ²

I

CY ^ - O— Y— Rf

(3)

with R ² , R ³ = alkyl, eg CH ₃ ; 2 <1 <16, eg 1 = 3; 1 <m, n <6;<p<200; 0 <r <50; X, Y = single bond, -CO-, C1-C6 alkylene; These perfluorinated grafts (1) to (3) have in common the presence of etheroxide bonds within the patella connecting the perfluorinated radical Rf to silicon.

To compensate for the absence of chemically stable perfluorinated POSs which can be obtained in a simple and economical manner, the Applicant has already proposed new linear or cyclic perfluorinated POSs meeting these specifications and comprising perfluorinated Gf grafts of formula:

in which m> 2 and Rf = perfluorinated residues; and possibly one or more other Gf grafts perfluorinated or not with a first condition according to which at least 60% of the Gf grafts are perfluorinated and a second condition according to which in the case where m = 2, then at least one other Gf graft is provided different in nature from that defined in the above formula. These POS can respond, eg to the following formula:

These POSs can be used in the formulation of antifoams of lubricants, anti-adhesion agents, agents for reducing surface tension, anti-fouling agents, oleophobic and / or hydrophobic agents or raw materials for the production of elastomers or films resistant to chemical attack and to solvents. These new perfluorinated POSs as well as their obtaining and their application are described in French patent application No. 95 09 269.

BRIEF EXPOSURE:

One of the essential objectives of the present invention is to improve the perfluorinated silicone (co-) polymers according to the prior art and in particular according to FR 95 09 269:

- by providing them with better attachment properties to substrates with regard to coating and / or impregnation applications, - and by improving their resistance to washing, to wear and to abrasion, in short by increasing their service life . It is indeed important that the perfluorinated silicone systems are not sensitive to external aggressions (solubilization / extraction due to washing or the action of abrasives), so as to preserve their desired properties of lowering the surface tension at the origin of their waterproofing, anti-stain and anti-soiling functions. In fact, the above-mentioned external aggressions have the direct impact of eliminating perfluorinated groups on the surface. However, we have seen above that this surface localization of said Rf groups is essential to their effectiveness.

Having set themselves this objective, among others, the inventors had the merit of highlighting after long and laborious research and experiments, and in a completely surprising and unexpected manner, that one could go in the direction improvement by proposing a crosslinkable silicone system, comprising POSs carrying perhalogenated Gf grafts, preferably perfluorinated, judiciously selected from perfluorinated esters of dicarboxylic acids capable of forming anhydrides (eg maleic acid). These Gf grafts are called bifid Rf grafts.

It follows that the present invention relates to a crosslinkable silicone composition which can be used, in particular, for the production of coatings and / or hydrophobic and / or oleophobic impregnations with low surface energy, of the type of those comprising: AT . at least one perfluorinated POS

. B. at least one crosslinker, perfluorinated or not, and capable of reacting with the

POS A; . VS . optionally at least one catalyst for the reaction (s) between A and B; . D. optionally one or more functional additives; characterized in that <POS A carries, per molecule:

- »of one or more perfluorinated Gf grafts identical or different between them and of formula:

(CH,) - CR O— Rf, o in which: the radicals R ¹ independently represent hydrogen or a CC ₆ alkyl

Rfi and Rf ₂ are perhalogenated radicals - preferably perfluorinated - and more preferably still a linear or branched perfluoroalkylated radical of formula:

(H) CqF, q— CF ₃ with q ^ O; or

(m) - CqF, q H with q Y 1 _;

- m ^≈ l to lO; - n = 0 to 4; - »of one or more crosslinking functions Fra identical or different between them, and in that the crosslinking agent B carries, per molecule, at least two crosslinking functions Frb, identical or different between them and capable of reacting with the POS A functions to ensure crosslinking. By way of legend for all the formulas given in this presentation, it should be noted that the free valences represented in bold ^ ~, are those which are attached directly or indirectly to the silicon of POS A or of the crosslinker B.

By low surface energy, according to the invention is meant values of total γ _s <15 mJ / m ² .

By resolutely choosing to implement a crosslinkable system and POSs substituted by perfluorinated Gf grafts of formula I of bifid type Rf or bisRf, the inventors provide a completely satisfactory solution to the problem of the attachment of hydrophobic and oleophobic fluorinated coatings. , on substrates. This also makes it possible to increase the durability of the effectiveness of surface fluorine with regard to the properties of resistance to aqueous and fatty substances, which it is desired that these fluorinated silicone coatings express at a high level and in a lasting manner.

In addition, without wishing to be bound by theory, it would seem that the bifid structure of the Gf grafts selected according to the invention, contributes to the establishment of an anisotropic organization, which promotes the hydrophobic and oleophobic action of the perfluorinated motifs. DETAILED DESCRIPTION OF THE INVENTION:

Still being perfluorinated Gf grafts, it should be noted that according to the invention, the monovalent residues Rfi and Rfî in formula I preferably correspond to -C _p F _2p -CF ₃ ; with p between 3 and 20; preferably between 5 and 20 and, more preferably still between 7 and 10.

In practice, it is also possible to use, for example, mixtures of Rf whose indices p are equal to 7, 8 or 9.

According to a variant, the POS A carries, per molecule:

- »of one or more perfluorinated Gfh grafts identical or different between them and of formula (1.1):

in which :

- R ¹¹ , Rf ₃ , m ', n' meet the same definitions as those given above for R ¹ , Rfi, m, n;

- Rh is a linear or branched alkyl radical, preferably linear in C6-C40 and more preferably in Cβ-C ₂ o.

- and optionally one or more identical or different Gh grafts between them and of formula (1.2):

O in which:

- R ¹² , m ", n" and Rhi, Rh ₂ correspond respectively to the same definitions as those given above for R ¹¹ , m ', n' and Rh. In addition to these specific perfluorinated units, the invention also relies on the ability to crosslink the composition it relates to. Thus, in accordance with a preferred method, the pairs of reactive functions Fra / Frb are chosen from the group comprising:

The reactive functions Fra / Frb of the first two lines of the table below refer to a crosslinking mechanism by hydrosilylation of Si-alkenyl units (advantageously C ₂ -Cιo) with Si-H units, in the presence of a metallic catalyst , preferably platinum; while the pairs of reactive functions Fra / Frb = COOR / oxazolidine and oxazolidine / COOR correspond to a crosslinking mechanism by opening the oxazolidine ring and reaction with the oxygen of the carboxyl group. The radical R of the group COOR may be hydrogen, an alkyl or a cation, for example NH 2 or Na ⁺ , linked to the carboxylate anion COO ^" . For more details on the reactions of oxazolidine / COOR functions, reference is made to following references:

M "Oxazolines. Their preparation, reaction and applications »

John A. FRUMP Chem. Rev, 71, 483 (197 1), a "The chemistry of 2-oxazolines" T.G. GANT and A.I. MEYERS

Tetrahedron 50 (8), 2297 (1994).

These two modes of crosslinking have the advantage that they are simple and economical to implement on an industrial scale. Thus, in these two modes, the catalysts used are common industrial catalysts, such as for example those based on platinum such as the Karstedt catalyst as regards hydrosilylation or as cadmium acetate as regards opening of oxazolidine cycle. These inexpensive catalysts are used in small quantities. In addition, the crosslinking kinetics are quite honorable, in particular as regards hydrosilylation.

The particular feature of the COOR / oxazolidine crosslinking system is that it can be used in the absence of a catalyst, thanks to thermal activation.

It will be observed that, in accordance with the invention, the POS A and the crosslinker B each comprise, per molecule, at least one reactive function Fra and Frb respectively. These functions Fra and Frb are complementary, that is to say they are capable of reacting with each other. This characteristic necessary for bridging AB is not exclusive of other modes of implementation in which the POS A and / or the crosslinker B would comprise on the same molecule complementary reactive functions capable of reacting with each other H / alkenyl (vinyl) and / or COOR / oxazolidine. But preferably, each molecule of POS A or of crosslinking agent B comprises non-complementary reactive functions, incapable of reacting with one another.

According to a first preferred embodiment of the invention, the POS A comprises Fra = H and the crosslinker B is a mono and / or a polysilane and / or a di and / or a polysiloxane comprising, per molecule, at least two Frb = C ₂ - C ₁₀ alkenyl, preferably vinyl. Preferably, B is an organodisiloxane oil, for example divinyltetramethyldisiloxane (DVTMS), and / or is chosen from polydiorganosiloxane oils, in particular from polydimethylsiloxane oils, which are functionalized with Frb = alkenyl, preferably Vi, in and / or at the end (s) of chains. In the context of the first embodiment of the composition according to the invention, the composition comprising one or more POS A more specifically corresponding to the following formula (IV) is chosen: (IV)

with

, 2

DR identical or different from each other - methyl, propyl or butyl; DR ³ identical or different from each other = linear or branched alkyl, preferably C6-C40, and more preferably C ₆ -C ₂₀ ; D o <p ', preferably 1 <p ¹ <100; D o <p ", preferably 0 <p"<500; D o <p ^ai , preferably 2 <ρ ^Ui <100; π o <p ^iv , preferably 0 <p ^iv <100; D o <p ^v , preferably 0 <p ^v <100; π o <p ^vi , preferably 0 <p ^vi <100. D ∑p ^{! at vi} + 2 = 5 to 600, preferably 50 to 300. In practice, we can have: p 'between 1 and 50 p "between 50 and 300 p""between 5 and 50 p ^{, v} between 0 and 50 p ^v between 0 and 50 p ^vl between 0 and 50. As a variant of this first embodiment, the POS A comprises Fra = C ₂ -C alkenyl preferably vinyl and the crosslinking agent B is a carrier of Frb = H, B being advantageously selected from organodisiloxane oils and / or polyhydrogenodiorganosiloxane oils functionalized with Frb = H in and / or at the chain end (s). In accordance with a second preferred embodiment of the composition according to the invention, the POS A comprises Fra = COOR and the crosslinker B is a hydrocarbon compound and / or a mono and / or a polysilane and / or a di and / or a polysiloxane comprising, per molecule, at least two Frb = oxazolidine. B is preferably a bis-oxazolidine of formula:

(V)

with X corresponding to an alkylene or to a POS. X = alkylene in this formula (V) more preferably still corresponds to divalent Cι-C ₂ o and, for example, C ₄ alkyl radicals.

To fix the ideas, it will be specified that the POS A of the composition can advantageously respond to the following formula (Vu): (SEEN)

in which: π W is a carboxylated hydrocarbon radical, preferably chosen from: ° the groups of formula (VD3) below:

C (R ¹ ) ₂ - n "'

in which :

- R ¹³ , m '", n'" meet the same definitions as those given above for R ¹ , m, n; - E ¹ , E ² correspond one and / or the other to -COOR as defined above, and in the case where E _\ or E ₂ ≠ COOR then E ¹ or E ² = R ¹³ ; ° linear or branched alkyls, preferably C ₂ -C ₂₀ , terminated by at least one carboxylated COOR and different from the groups of formulas (Vπi); π R ⁴ identical or different from each other = methyl, propyl or butyl; Ώ R ⁵ identical or different from each other = linear or branched alkyl, preferably C ₆ -C ₄₀ , and more preferably still C _Ô - C ₂ o; α R identical or different from each other = H, cation or protective group, preferably chosen from alkyls and / or alkylsilanes, D o <r ', preferably 1 <r ¹ <100, and even more preferably 1 < r ¹ <50, D 0 <r "> 0, preferably, 0 <r"<500, and more preferably still 50 ≤ r '≤ 300, D 0 <r "', preferably, 2 <r ¹ "< 100, and more preferably still 5 <r ^Hi <50, π 0 <r ^ιv , preferably, 0 <r ^ιv <100, and more preferably still 0 <r ^iv <50, π o <r ^v > 0, preferably, 0 <r ^v <100, and more preferably still 0 <r ^v <50, D o <r ^vι , preferably, 0> r ^vl <100, and more preferably still 0 <r ^vi <50 As a variant of the second preferred embodiment of the composition according to the invention, mention may be made of the case where the POS A comprises Fra = oxazolidine and where the crosslinking agent B is:

Δ a diacid or derivative of formula (VI): ^{R00C— x} COOR _in which X ¹ is a hydrocarbon radical, preferably an alkylene in

Δ and / or a POS carrying, per molecule, of at least two Frb = -COOR and optionally of one or more perhalogenated, preferably perfluorinated Gf grafts, of formula identical to formula (I) given above. According to an advantageous characteristic of the invention common to the two preferred embodiments of the composition defined above, the POS A and optionally the crosslinker B may comprise (or may comprise), per molecule, in addition to the perhalogenated grafts - preferably perfluorinated - Gf of formula (I), perhalogenated grafts - preferably perfluorinated - Gf 'of formula (D):

(π)

- (iLJ— Rf, in which: t> 2 and Rf ₃ corresponds to the same definition as that given above for Rfi and Rf ₂ .

In these embodiments and their variants, the preferred POSs from which POS A is capable of being selected are, in practice, the linear POSs which can possibly have up to 50% by weight of ramifications (units other than siloxy units D) cyclic polymers or three-dimensional polymers (resins comprising T and / or Q siloxyl units). However, in the context of the invention, it is very special to retain linear POS essentially consisting of D patterns.

As regards the basic POSs, precursors of the abovementioned grafted POSs, they are preferably linear polyorganohydrogensiloxanes.

Various chemical routes can be envisaged for the functionalization of these precursors of POS A, or even B. The choice of the suitable route is made as a function of the nature of the group to be grafted onto the silicone chain. According to the invention, preference is given to the hydrosilylation of alkenyl units with SiH units.

The functional features of the precursors have the effect that the POS A and the cross-linking agents B of the composition according to the invention can be defined through their production characteristics.

Thus, POS A is preferably obtained from POS chosen from polyalkylhydrogenosiloxanes, the SiH units of these POS then being at least partly used for the hydrosilylation of olefinic precursors:

• of all or part of the Gf grafts and, where appropriate, Gfh, Gh Gf ', • optionally of groups carrying at least one radical

COOR or capable of being substituted by at least one COOR radical,

• optionally of groups carrying at least one oxazolidine radical, or capable of being substituted by at least one oxazolidine radical, • optionally of groups carrying at least one crosslinking function Fra = alkenyl, preferably C ₂ -Cιo and more preferably still vinyl or capable of being substituted by at least one function Fra = alkenyl, preferably C ₂ -Cιo, and more preferably still vinyl, • and optionally of alkyl groups R ³ , R ⁵ as defined above, in the presence an effective amount of metal hydrosilylation catalyst, preferably based on platinum.

As regards crosslinking agent B, it can advantageously consist of a POS chosen from polyalkylhydrogenosiloxanes - preferably polymethylhydrogenosiloxanes - the SiH units of these POSs then being at least partly used for the hydrosilylation of olefinic precursors: of groups carrying d '' at least one crosslinking function Frb = alkenyl preferably in C2-do and more preferably still vinyl or capable of being substituted by at least one function

Frb = alkenyl, preferably C ₂ -do and more preferably vinyl; and / or groups carrying at least one crosslinking function Frb = COOR or capable of being substituted by at least one function Frb = COOR; and / or groups carrying at least one crosslinking function Frb = oxazolidine or capable of being substituted by at least one function Frb = oxazolidine; optionally all or part of Gf grafts and, where appropriate, Gfh, Gh, Gf; and optionally alkyl groups R ³ , R ⁵ as defined above; in the presence of an effective amount of metal hydrosilylation catalyst, preferably based on platinum. In cases where one only grafts by hydrosilylation first, only a part of the Gf or Glh, Gh, GF grafts, the contribution of the missing part can be carried out in one or more grafts involving a mechanism any chemical reaction.

This functionalization by segments can also be used for the other substituents Fra, Frb, alkyl of compounds A and B.

According to another of these aspects, the present invention relates to the perfluorinated silicone composition as described above, in crosslinked form.

The present invention also relates as new industrial products: - 1 - POS A carriers, per molecule, of one or more Gf grafts as well as one or more crosslinking functions Fra = oxazolidine,

- 2 - POS A carriers, per molecule, of one or more Gf grafts as well as one or more Gh grafts, - 3 - POS A carriers, per molecule, of one or more Gf grafts as well as one or more Gfh grafts;

- 4 - POS A carriers, per molecule, of one or more Gf grafts as well as one or more Gh grafts and one or more Gfh grafts; - 5 - POS A carriers, per molecule, of one or more Gf grafts, of one or more crosslinking functions Fra = oxazolidine and / or

COOR, and possibly one or more Gh and / or Gfh grafts.

Thanks to the particular nature of the perfluorinated grafts of POS A and optionally of the crosslinking agent B, combined with a crosslinking ability, the compositions according to the invention make it possible to impart, in a lasting manner, a low surface tension to the solids to which they are applied. or in which they are contained. These compositions thus provide oil properties and / or hydrophobicity stable over time. This result is particularly advantageous and interesting for applications such as coatings, finishes or impregnations: ° of textiles, ° of buildings (plasters, paints, anti-graffiti paints, varnishes)

° or any other article to protect against stains and soiling and to waterproof (eg "anti-fouling" paints for boats). These fluorinated silicone compositions according to the invention can also be used in the formulation of mastic, jointing and sealing material, lubricant, non-stick agent, anti-foaming agent, anti-grease agent.

The lowering of the surface tension induced by the fluorinated silicone compositions according to the invention, that is to say the oleo and / or hydrophobicity properties, can be adjusted by controlling the proportions of grafted D units or not by fluorinated and / or alkyl units. This corresponds to the variation of the indices p ¹ to p ^vι and r 'to r ^vl in the formulas (IV) and (VH) above of POS A.

The functional additives D differ according to the applications envisaged for the compositions.

In the case where the composition is intended to be used for the production of fluorinated coatings and / or impregnations on textile supports, the functional additives D can be for example:

- thermally condensable resins to improve dimensional resistance, resistance to washing or even provide a certain rigidity;

- softeners which give a soft touch, improve the behavior of the garment and favor mechanical treatments (emery, scraping, calendering);

- antistatic agents which facilitate the flow of electrostatic charges accumulated by textiles during the various drying and polymerization operations; - flame retardants which reduce flammability and prevent the spread of the flame;

- fungicidal and bactericidal agents that protect against mold and rot;

- products which are commonly referred to as extenders, which can be, for example, melamine resins modified with fatty acids, mixtures of waxes and zirconium salts and which, in combination with fluorinated resins, significantly improving the properties in certain cases.

The compositions according to the invention are prepared by mixing the various constituents A, B, optionally C and D. Before being used or incorporated in use formulations, these compositions can be in solution, in emulsion or even in the form melt.

According to another aspect of the invention, the POS A according to the invention are prepared by hydrosilylation of olefin precursors having at least one terminal double bond, of the various grafts or substituents envisaged for these POS A, with the exclusion of vinyls, it that is to say: Gf and where appropriate Gfh, Gh or Gf '; groups carrying at least one COOR radical or capable of being substituted by at least one COOR radical; ^ groups carrying at least one oxazolidine radical or capable of being substituted by at least one oxazolidine radical; of groups bearing at least one crosslinking function Frb = preferably C ₂ , C ₁₀ and alkenyl more preferably vinyl, or capable of being substituted by at least one Frb = alkenyl, preferably C ₂ -C 10 and more preferably vinyl,

^ and alkyl groups of the type of those corresponding to R ³ or R ⁵ as defined above. This mode of grafting perfluorinated, alkylated or crosslinking functionalities is also preferred, in the case where the crosslinking agent B is also a POS carrying SiH units.

These hydrosilylations take place, in a manner known per se, in the presence of an effective amount of metallic industrial catalyst, chosen from compounds based on nickel palladium or platinum, preferably based on platinum. This can for example be a Karstedt catalyst, advantageously used in small quantities eg of the order of 10 to 50 ppm relative to the POS compounds considered, before hydrosilylation (SiH oil). Hydrosilylation is a simple technique well known to those skilled in the art. It benefits from rapid kinetics and makes it possible to achieve particularly high yields and conversion rates of SiH units. The hydrosilylation conditions are conventional and therefore easily determinable by a person skilled in the art. In practice, hydrosilylation takes place in as many phases as there are different olefinic reactants. The reaction medium is stirred and brought to a temperature between 50 and 150 ° C. The reaction takes place at atmospheric pressure and generally over a period of several hours. The conversion rate of the SiH patterns is greater than 99% in number. We have seen that the grafting of a particular substituent, for example: Gf, Gfh, Gh, Gf ', Fra, Frb or long alkyls, can be broken down into several stages. The first of these steps is a hydrosilylation, by the SiH units of POS, of a precursor of the substituent corresponding only to a part of it. We then connect to this first link fixed by hydrosilylation on the main chain of the POS, one or more other links or spacing compounds until the graft or the substituent in its entirety is obtained.

The connection of the different links to each other can be carried out by various known chemical reaction mechanisms, e.g. esterification, addition, substitution ...

In the case of Gf, Gfh, Gh and Gf 'grafts of formula (I), it is possible to carry out the grafting by first fixing by hydrosilylation on the POS, a radical of which one of the ends comprises an ethylenic unsaturation and the other end of which has the two carboxyl functions in the form:

- COOH,

- COOR ', with R' = hydrocarbon radical, - COO X ^* , with X = alkali metal cation

- or ammonium.

These two carboxyl functions can also be in anhydride form. It is easy to react on these reactive carboxyl or anhydride functions, intermediate links or terminal links carrying the functionality or functions that one seeks to graft onto the POS. Thus, in the case where we have to deal with a first link with an anhydride end, it is conceivable:

- subjecting at least part of the anhydride functions attached to the POS, to hydrolysis and / or to salification so as to generate free carboxylic ends and to then esterify at least part of said ends, using reagents allowing to build the plugins in their entirety.

-> and / or to react directly the anhydride functions with the reagents making it possible to construct the grafts in their entirety. Regarding vinyl-functional POS reagents, they are obtained by a hydrosilylation method, which differs somewhat from that mentioned above, in the measurement where the hydrosilylated unsaturated unit is not of alkenyl but alkinyl type and where the catalyst is advantageously not based on platinum. For example, crosslinker B of the divinyltetramethyldisiloxane type is prepared by the action of acetylene on dihydrogenotetramethyldisiloxane. Among the POS which can be used as starting materials for obtaining POS A and optionally POS B crosslinking agents, mention may be made, by way of examples, of linear POS such as polymethylhydrogenosiloxanes comprising from 10 to 500 D units. of SiMeH or SiMeH and SiMe _{2 type} , or cyclic POSs such as tetramethylcyclosiloxane D'4. According to another of these aspects, the present invention relates to a two-component precursor system of the silicone composition as described above, characterized in that it comprises two distinct parts 1 and 2, intended to be mixed to form the composition, l one of these parts 1 or 2 comprising POS A or crosslinker B and optionally a catalyst C and / or a crosslinking inhibitor D.

Once mixed, parts 1 and 2 of the two-component system form a perfluorinated silicone composition ready for use, which can in particular be applied to a support by any suitable coating or spreading means (for example doctor blade or cylinder) . The invention also relates, in another of these objects, to a process for producing hydrophobic and / or oleophobic coatings and / or impregnations on a support, this process being characterized in that it consists essentially in: preparing and / or using a composition as defined above or obtained from the two-component system as defined above, applying this composition to a support so as to obtain a film and / or to impregnate it,

> optionally evaporating the solvent in the case where the composition is in the form of a solution; to ensure that the conditions, in particular of temperature and pressure, are met for crosslinking to take place. The support considered can be a textile or any other solid material, such as e.g.: metal, cement, concrete, wood, plastic, composite, etc.

Application techniques are based on general knowledge of each particular area of use. The following examples provide some illustrations in this regard. INDUSTRIAL APPLICATION:

The present invention also relates to the products or formulations in which the composition to which it relates can be incorporated. These include, among others:

- coating precursors,

- coated,

- paints ("antifouling" paints ...),

- varnish, - lubricants,

- surface tension lowering agents,

- anti-fouling agents,

- non-stick agents,

- anti-foaming agents, - oleophobic and / or hydrophobic agents,

- raw materials for the production of elastomers or films resistant to chemical attack and to solvents,

- textile finishes.

Also included in the context of the invention are films and / or coatings made from the composition as defined above.

EXAMPLES:

EXAMPLE I PREPARATION OF CROSS-LINKABLE SILICONE COMPOSITIONS

BY HYDROSILYLATION SiH / SiVi AND BASED ON DIFFERENT POS A AND A CROSSLINKER B = TETRAMETHYLDJTVTNYLDISILOXA E - REALIZATION OF

CROSSLINKED COATINGS FROM SUCH COMPOSITIONS

1.1 PRODUCTS IMPLEMENTED a) POS A

The POSs used are POSs obtained by conventional redistribution reactions and comprising the following reasons:

D '= MeHSiθ2 / ₄

The base SiH oil corresponds to the formula: M DsoD'soM.

The vinyl precursor of the Gf graft used corresponds to the following formula:

The hydrosilylation reaction used for the grafting is as follows:

MD ₅₀ D _'50 M

MDΛAM

F ₁₇ C ₈ H,

Rf Legend: D 'corresponds to D in the following

Gf Octyl radicals (R ³ or R ⁵ ) are grafted in the same way starting from octenyls. The POS A products prepared are described in Table 1 below.

b) Crosslinker B is

c) Catalyst C of the composition is a Karstedt catalyst d) The composition comprises as functional additive (D) a crosslinking inhibitor: EthynylCycloHexanol (ECH)

Samples 3, 4, 5, 6 and 7 are used below to make coatings. The control sample is a fluorine-free reference oil (control).

1.2 PREPARATION OF COATINGS

The coatings were prepared in the melt and in the solvent phase (C4F9OCH3), in the presence of ECH, on polyester sheets or glass. The solvent is evaporated beforehand under vacuum, then the system is crosslinked in temperature at 90 ° C. Cross-linking is followed by IR in attenuated total reflection (disappearance of the SiH band). The contact angles are then measured using a Rame-Hart A-100 goniometer interface with image analysis software. The probe liquids used are water and diiodomethane. The values of the angles are averages over 10 drops for each sample, then a computerized treatment makes it possible to deduce the surface energy of the coating.

1.3 RESULTS

1.3.1 Influence of the support and the application method fCf Table 2 below)

From oil 5, the values obtained on glass or on polyester are of the same order of magnitude. These values are lower than for a conventional silicone (20-23 mJ / m ² ).

1.3.2 Influence of fluorine content and network size

All the oils prepared containing a high proportion of fluorine, the results obtained are of the same order of magnitude: see Table 3 below. The introduction of octyl patterns (ech 6) increases the surface energy.

1.3.3 Stability of coatings

We examine how the surface energies of coatings change after a more or less long soaking in a polar liquid, demineralized water. These tests were carried out on three functionalized oils and on the control: Table 4 below giving the results obtained.

The values obtained with samples 6 and 3 indicate that after soaking in water, impurities are present on the coating (mineral salts), and lead to higher values than silicone alone. A simple wash with acetone allows to recover the initial values. 1.3.4 One-component system

The system is simplified by effecting the functionalization of the oil with fluorinated patterns during crosslinking. The relative reactivities of B and allyl Rf are different.

The coatings are produced starting from solvent and bulk samples. An acetone wash is optionally carried out after crosslinking for 2 hours at

90 ° C.

Table 5 below giving the results obtained.

Surface energies close to that obtained by the functionalization route are obtained. The stability of these coatings has not been evaluated.

EXAMPLE II PREPARATION OF CROSSLINKABLE SILICON COMPOSITIONS BY OXAZOLIDINE / COOR REACTION AND BASED ON DIFFERENT POS A AND A B = BIS-OXAZOLIDINE CROSSLINKER

II.1 PREPARATION OF RF SILICONE OILS - POS (A) - / CARBOXYLIC ACID The undecylenic acid was previously protected with HexaMethylDisilazane before grafting onto silicone oil M DsoD'soM. The preceding bis-Rf and octyl patterns are also introduced into this oil:

PROTECTION:

Me Me CF ₃ COθH

• I

(CH ₂ ) ₈ -COOH + ι / 2Me - S Sii --NN —- - SSii —- Me \ (CH,) ₈ - COOSiMe ₃ ι H 1

Even

GRAFT:

O C-0- (CH ₂ ) ₂ -C _a F ..

C-0- (CH ₂ ) ₂ -C ₈ F ₁₇

[Pt]

MD ^ D '^ ^ (CH ₂ ) g-COOSiMe ₃ MD n DRf D∞OSi θS DOct M

-'SO

^ (CH ₂ ) ₅ - CH ₃

PROTECTION :

H, θ

MD ₅₀ DR ^f D∞ ° SiMe3 _D Ool _M MD ₅₀ D ^Rf D ^COOH D ° ^ct M The protection of undecylenic acid was carried out according to the procedure of patent EPI 96169. From this protected acid, octene and bis Rf graft, three oils were prepared:

The deprotection of the COOSiMe3 groups with water was carried out without problem from the three preceding oils.

π.2 PREPARATION OF THE BIS OXAZOLIDINE CROSSLINKER The water-soluble bis-oxazolidine used is as follows:

It has been prepared in three different ways described in the previous literature. : - from adipic acid and ethanolamine

- from methyloxazoline, by lithiation

- from adiponitrile and ethanolamine

The catalyst used in the latter case is cadmium acetate. A yield of distilled product of 60% is obtained after 25 h of reaction. A solvent common to the crosslinking agent and to the functional oils was sought. Only acetone almost completely solubilizes oils.

In the same way as for Example I, the stability in water of the coatings before and after crosslinking was examined. Acetone washing is carried out on the samples after passage through water. Table 6 below gives the results obtained.

POS A samples are stored in the air.

Table 2

* The samples are washed 3 times with acetone

Table 6

Crosslinking provides very interesting surface energy stability. The oil with the fewest patterns (ech 10) leads to the lowest surface energies.

Claims

CLAIMS:

1 - Crosslinkable silicone composition which can be used, in particular, for the production of hydrophobic and / or oleophobic coatings and / or oleophobes with low surface energy, of the type of those comprising: AT . at least one perfluorinated POS

. B. at least one crosslinker, perfluorinated or not, and capable of reacting with POS A; . VS . optionally at least one catalyst for the reaction (s) between A and B;

. D. optionally one or more functional additives; characterized in that <POS A carries, per molecule:

in which :

- the radicals R ¹ independently represent hydrogen or a Cι-C ₆ alkyl

- Rfi and Rf ₂ are perhalogenated radicals - preferably perfluorinated - and more preferably still a linear or branched perfluoroalkylated radical of formula:

(H) CqF ₂ q— CF ₃ with q ^ O; or

(m) - CqF ₂ q H with q Y 1 _;

- m ≈ l to lO;

- n = 0 to 4; - one or more Fra crosslinking functions which are identical or different between them, <and in that the crosslinking agent B carries, per molecule, at least two crosslinking functions Frb, identical or different from each other and capable of reacting with the POS A functions to ensure crosslinking.

2 - Composition according to claim 1, characterized in that the POS A is carrier, per molecule:

-> one or more perfluorinated Gfh grafts identical or different between them and of formula (1.1):

in which :

- R ¹¹ , Rf ₃ , m ', n' meet the same definitions as those given for R ¹ , Rfi, m, n in claim 1.

- Rh is a linear or branched alkyl radical, preferably linear in C ₆ -C ₄₀ and more preferably in Cδ-C ₂₀ .

O in which:

R ¹² , m ", n" and Rhi, Rh ₂ correspond respectively to the same definitions as those given above for R ¹¹ , m ', n' and Rh.

3 - Composition according to claim 1 or 2 characterized in that the pairs of reactive functions Fra / Frb are chosen from the group comprising:

4- Composition according to any one of claims 1 to 3, characterized in that the POS A comprises Fra = H and in that the crosslinker B is a mono and / or a polysilane and / or a di and / or a polysiloxane comprising, per molecule, at least two Fra = Vi; B preferably being an organodisiloxane and / or a polydiorganosiloxane.

5 - Composition according to any one of claims 1 to 4 characterized in that it comprises one or more POS A corresponding to the following formula (IV):

(IV)

[ ^{(R iθ} _1/2 τf ^{R2GfSi (} ^ ^(R2) ₂ ^Siθ - ^ ^R ^

^J T ii "i" v „w

PPPPP with π R ² identical or different from each other = methyl, propyl or butyl; o R ³ identical or different from each other = linear or branched alkyl, preferably C6-C40, and more preferably Cβ-C ₂₀ ; D o <p ', preferably 1 <p ¹ <100; o 0 <ρ ^{! i} , preferably, 0 <p "<500; D 0 <p ^{i! i} , preferably, 2 <p ^πi <100; D 0 <p ^iv , preferably, 0 <p ^iv <100 ; π 0 <p ^v , preferably 0 <p ^v <100; D 0 <p ^vl , preferably 0 <p ^vl <100. o op ^{! at vi} + 2 = 5 to 600, preferably 50 to 300.

6 - Composition according to any one of claims 1 to 5, characterized in that the POS A comprises Fra = COOR and in that the crosslinker B is a hydrocarbon compound and / or a mono and / or a polysilane and / or a di and / or a polysiloxane comprising, per molecule, at least two Frb = oxazolidine.

B is preferably a bis-oxazolidine of formula:

(V)

[*] with X corresponding to an alkylene or to a POS. 7 - Composition according to any one of claims 1 to 6, characterized in that it comprises POS A corresponding to the following formula (Vu):

(vπ)

with α W corresponding to a ball joint consisting of a hydrocarbon radical, preferably chosen from: ° the groups of formula (Vπi) below:

in which: - R ¹³ , m '", n'" meet the same definitions as those given above for R ¹ , m, n; - E ¹ , E ² correspond one and / or the other to -COOR as defined above, and in the case where Ei or E ₂ ≠ COOR then E ¹ or E ² = R ¹³ ; ° linear or branched alkyls, preferably C ₂ -C ₂₀ , terminated by at least one carboxylated COOR and different from the groups of formulas (VHI); α R ⁴ identical or different from each other = methyl, propyl or butyl; DR ⁵ identical or different from each other = linear or branched alkyl, preferably C6-C40, and even more preferably CÔ-

C ₂ o; π R identical or different from each other = H, cation or protective group, preferably chosen from alkyls and / or alkylsilanes, D o <r ', preferably 1 <r ¹ <100, and even more preferably 1 ≤ r'≤ 50, α o ≤ r "> 0, preferably 0 <r"<500, and more preferably still 50 ≤ r '≤ 300, D o <r ¹ ", preferably 2 <r"'< 100, and more preferably still 5 <r ^Hi <50, π o <r ^ιv , preferably, 0 <r ^ιv <100, and more preferably still 0 <r ^iv <50, D o ≤ r ^v > 0, preferably , 0 <r ^v <100, and more preferably still 0 <r ^v <50, D o <r ^vl , preferably, 0> r "≤ 100, and more preferably still 0 <r ^vi <50

8 - Composition according to any one of claims 1 to 6, characterized in that the POS A comprises Fra = oxazolidine and in that the crosslinking agent B is:

Δ a diacid or derivative of formula (VI): ^{R00C— xc} OOR _in which X ¹ is a hydrocarbon radical, preferably a Cι-Cι ₂ alkylene.

Δ and / or a POS carrying, per molecule, at least two

Frb = -COOR and optionally one or more perhalogenated, preferably perfluorinated Gf grafts, of formula identical to formula (I) given in claim 1.

9 - Composition according to any one of claims 1 to 8 characterized in that the POS A is obtained from POS chosen from polyalkylhydrogenosiloxanes, the SiH units of these POS then being at least partly used for the hydrosilylation of precursors olefinic: • of all or part of Gf grafts and if necessary Gfh, Gh Gf '

• optionally groups carrying at least one COOR radical or capable of being substituted by at least one COOR radical,

• optionally groups carrying at least one oxazolidine radical, or capable of being substituted by at least one oxazolidine radical. • optionally of groups carrying at least one Fra = alkenyl crosslinking function, preferably vinyl or capable of being substituted by at least one Fra = alkenyl function, preferably vinyl, • and optionally of alkyl groups R ³ , R ⁵ such as defined in claims 4 and 7, in the presence of an effective amount of metal hydrosilylation catalyst, preferably based on platinum.

10 - Composition according to any one of claims 1 to 9 characterized in that the crosslinking agent B is a POS obtained from POS chosen from polyalkylhydrogenosiloxanes - preferably polymethylhydrogenosiloxanes - the SiH units of these POS then being at least in part used for the hydrosilylation of olefinic precursors:

- of groups carrying at least one crosslinking function Frb = alkenyl or capable of being substituted by at least one function

Frb = alkenyl, preferably vinyl;

- And / or groups carrying at least one crosslinking function Frb = COOR or capable of being substituted by at least one function Frb = COOR; - And / or groups carrying at least one Frb - oxazolidine crosslinking function or capable of being substituted by at least one Frb = oxazolidine function;

- possibly all or part of Gf grafts and if necessary Gfh, Gh, Gf; - And optionally of alkyl groups R ³ , R ⁵ as defined in claims 4 and 7 in the presence of an effective amount of metal hydrosilylation catalyst, preferably based on platinum.

11 - Crosslinked composition characterized in that it is obtained from the composition according to any one of claims 1 to 10.

12 - Constituent of the composition according to claim 1, characterized in that it is chosen from the group comprising:

- 1 - POS A carriers, per molecule, of one or more Gf grafts as well as one or more crosslinking functions Fra = oxazolidine, - 2 - POS A carriers, per molecule, of one or more Gf grafts as well as one or more Gh grafts, - 3 - POS A carriers, per molecule, of one or more Gf grafts as well as one or more Gfti plugins; - 4 - POS A carriers, per molecule, of one or more Gf grafts as well as one or more Gh grafts and one or more Gfh grafts;

- 5 - POS A carriers, per molecule, of one or more Gf grafts, of one or more crosslinking functions Fra = oxazolidine and / or COOR, and optionally one or more Gh and / or Gfh grafts.

13 - Process for producing hydrophobic and / or oleophobic coatings and / or impregnations on a support, characterized in that it essentially consists in preparing and / or using a composition according to any one of claims 1 to 11 or obtained from the two-component system according to claim 14;

> applying this composition to a support so as to obtain a film and / or to impregnate it;

> optionally evaporating the solvent in the case where the composition is in the form of a solution;

> to ensure that the conditions, in particular temperature and pressure, are met for crosslinking to occur.

14 - two-component precursor system of the silicone composition according to any one of claims 1 to 11, characterized in that it comprises two separate parts 1 and 2, intended to be mixed to form the composition, one of these parts 1 or 2 comprising POS A or crosslinker B and catalyst C.

15 - Precursors of coatings, coatings, paints, varnishes, characterized in that they comprise the composition according to any one of claims 1 to 11.