MXPA97003560A

MXPA97003560A - Functionalized polygonganosiloxanes and one of their preparation procedures

Info

Publication number: MXPA97003560A
Application number: MXPA/A/1997/003560A
Authority: MX
Inventors: Priou Christian; Jost Philippe; Peignier Michel
Original assignee: Rhone Poulenc Chimie
Priority date: 1994-11-18
Filing date: 1995-11-15
Publication date: 1997-08-01

Abstract

The present invention relates to multifunctional polyorganosiloxanes comprising per alpha molecule, on the one hand, at least one functional siloxyl unit (I) :( R) to Y Si (O) (3-a) / 2, wherein R is especially a C 1 -C 6 alkyl radical, Y is a C 1 -C 15 alkoxyl radical and a = 0.1, 2, on the other hand, at least one other functional siloxyl unit (II) :( R) b W Si (O) ( 3-b) / 2, wherein W is hydrogen or a group bonded to silicon by a Si-C bond, selected from the groups: alkyl, aralkyl or halogenated or polyhalogenated aryl, polyether oxide, epoxidized alkyl, alkoxy alkyl, hydroxylated alkyl, carbonyl or esterified, phenolic, and alkoxysilyl, and optionally at least one (III) :( R) c (H) dSi (O) [(4- (c + d)] / 2 where C = 0.1 , 2o3, d = 0o1 and c + d is < -3. The alkoxy functionality Y is introduced on an appropriate polyhydrogen-organosiloxane by a dehydrogenation / condensation reaction from the alcohol from which Y is derived, and then the functionality W by a hydrosilylation reaction from the olefinic compound from which it derives W. Multifunctionalized polyorganosiloxanes can be used as anti-adhesion modulators in silico compositions

Description

FUNCTIONALIZED POLYGONGANOSILOXANES AND ONE OF THEIR PREPARATION PROCEDURES The field of the present invention is that of the polyorganosiloxanes comprising various functionalities provided by substances of the silica and conferring to the silicone polymers specific properties, for example, anti-adhesion, lubrication or reinforcement sought in the applications of silicones . More precisely, the present invention relates to a multifunctional polyorganosilaxane, whose functionalities are carried for siloxyl reasons, by means of the SiC or SiOC bond. The present invention also relates to a process for functionalizing polyorganosiloxanes, which makes it possible, in particular, to obtain the multifunctional polyorganosiloxanes which form the subject of the present invention. Classically, the functionalization of the polyorganosiloxanes can be carried out by substitution of the hydrogens carried by the silica atoms of the chain. According to a first route, this substitution can consist of a hydrosilylation reaction between a polyorganohydrogenosiloxane and an olefinic reagent, carrying at least one Pi double bond, which can react with the hydrogen according to an addition mechanism. Hydrosilylation is a reaction well known in the technical field under consideration. Customarily, this reaction is catalyzed with platinum. It is widely described in the literature. In relation to this, one can refer, for example, to the article by V. M. KOPILOV AND COLL. , Z. Obsch Khim. , vol 57 (5), (1987) p. 1117-1127. In this first way, all the atoms of the available hydrogen silica are replaced by organic motifs by means of the SiC bonds, whose organic motifs are provided by the olefinic reagent (s). An illustration, among others, of hydrosilylation is given by European Patent Application No. 504,800, which describes the addition of a polyoxyalkylene substituted by an olefinic (vinyl) group on a polydi-ethylhydrogensiloxane of the formula: Me3SiO (Me2SiO) 157 (MeHSiO) 21 SiMe3 (Me = CH3), in the presence of an onocarboxylic ester of a solvent of the alkanediol type. In this case, it clearly appears that a single type of functionalization can be planned and only the groups that can be replaced by means of olefinic residues can be grafted onto the polyorganosiloxane. A second way of functionalization is that according to which the silicas of the polyorganosiloxane in question are replaced by means of functional residues linked to the latter, thanks to SiOC bridges. The reactions that can be planned to do this, for example, are those that involve alpha-s7-ega-chloros-loxanes and alcohols or then also polyorganohydrogensiloxanes and alcohols according to a mechanism of dehydrogencondensation. These dehydrogencondensation reactions, also described as organohydrogen-siloxane alcohols, are described above all in S. KOAMA and Y. HUMEKI, Journal of Applied Polymere Science Vol 21 (277), pages 863-867. This article refers to polymethylhydrogensiloxane in the presence of alcohol of the methanol or ethanol type and of a catalyst selected from the bases and certain metal chlorides (Lewis acids). The solvent that is put into work is benzene. In this way, the authors obtain a polyalkoxy-ethylsiloxane also endowed with a single functionality.

There is also recourse to the dehydrogen condensation in the invention described in US Patent No. 5 310 842 and its corresponding EP-A-0 475 440 relating to alkoxy-substituted linear polyorganosiloxanes. These products can be multifunctional and comprise, on the one hand, siloxyl motifs located in the chain or chain ends, equipped with a higher alkoxy function having from 4 to 30 carbon atoms and, on the other hand, siloxyl units, also located in the chain at chain ends, equipped with hydrocarbon radicals which can each represent a functional moiety consisting of an alkyl group having a high carbon condensation which can reach C15 or an alkenyl group at 2-15 comprising a double link; that type of multi-functional linear polyorganosiloxanes are excluded from the scope of the present invention. The catalyst that is put into work in this dehydrogencondensation is platinic in nature (chloroplatinic acid). All the starting methylhydrogensiloxylas functions are converted (conversion rate higher than 99%) into substituted siloxyl units. The lateral alkoxylated chains are involved in the counting of the polyorganosiloxanes with other products, such as, for example, organic polymers with which they are used in the final applications. Although the authors claim that these alkoxylated polyorganosiloxanes have a good resistance to hydrolysis, they can afford to doubt, taking into account the non-negligible sensitivity of the oxygen bridge in this respect. This review of the prior art shows that the multifunctional polyorganosiloxanes are not very numerous. This type of product would be very appreciable in certain uses of silicones, because it is evident that the multifunctionalization only increases the potential of these products, already very efficient. The contribution of multiple functionalities through grafting, would also seek the undeniable advantage of being able to build silicones on measure, specifically adapted to the applications that are to be achieved. Under these conditions, one of the essential objects of the present invention is that of providing a functionalized polyorganosiloxane, in particular multi-functionalized and more particularly still, comprising at least two different functionalization sites (or motifs) siloxyl, each carrying a type of functionality corresponding to a plurality of functional species.

Another essential objective of the invention is that of providing a polyorganosiloxane which can be obtained simply and cheaply. Another essential objective of the invention is that of providing a process for preparing polyorganosiloxanes which simultaneously exhibit various types of functions provided by grafting, in particular two types of functions. This procedure must be easy to implement and be of low cost, both on the level of raw materials to be used, and on the material resources, energy and time needed. It is seeking to satisfy those objectives, which the Applicant discovered in a totally surprising and unexpected way, after many studies and experiments, that contrary to what KOAMA and HUMEKI teach, the alcoholysis of the polymethylhydroxy oxoxanes, leads under certain conditions, to alkoxy siloxyl motifs -substituted and hydrogenosiloxyl motifs whose hydrogengene did not react, according to a particular stoichiometry. In relation to the foregoing, the present invention, which allows achieving the objectives indicated above, among others, is related, as a new product per se, to a functionalized polyorganosiloxane, and more particularly multifunctionalized, comprising, per molecule: fa - on the one hand, at least one functional siloxyl compound of the formula: (I) (R) _ Y Yes (O) wherein: * a = 0, 1 or 2 * R is a monovalent hydrocarbon radical selected from straight or branched alkyls having from 1 to 6 atoms, in particular methyl, ethyl, propyl, butyl and / or aryls and in particular femlo, methyl which are more particularly preferred; The radicals R are identical or different when a = 2. * Y is a linear or branched alkoxyl radical selected, preferably, from the alkoxy groups in C-1-C-, methoxy, ethoxy and (iso) propoxy they are more particularly preferred. beta. - and on the other hand, it was less a functional siloxyl motif of formula: (II) (R) bw if (O) 3 _ b in which: * b = 0, 1 or 2, * R has the same definition as that given above for the substituent R of the motif (I) and it may be identical or different from the latter. * W is hydrogen or a monovalent hydrocarbon radical having from 2 to 30 carbon atoms and optionally S and / or O atoms and constituting a functional moiety, linked to the silica by a Si-C bond; this residue is selected from the following groups: (i) an alkyl, aralkyl or aryl group substituted by one or more halogen atoms (s) and / or by a mono- or poly-halogenoalkyl radical, (2i) a polyether group oxide of formula (R 1 O) e R 2 with R 1 representing an alkylene group, and R 2 representing a hydrogen atom or an alkyl group and e = 1 to 5, (3i) an epoxy group resulting from the attachment of an oxygen with two carbon atoms belonging to a cycloalkyl or alkenyl alkyl group, (4i) an alkoxyalkyl or aryloxyalkyl group, (5i) a mono- or poly-hydroxylated and / or mono- or poly-carbonyl and / or mono alkyl group - or poly-esterified, (6i) a closely concealed phenolic group or a group derived from a mono- or di-hydroxylated benzophenone, (7i) an alkoxysilyl group, preferably trialkoxysilyl; the bda - and optionally at least one siloxyl (III) motif of the following formula: (R) c (H) d If (0) 4 _ (C +) (III) 2 in which: * c = 0, 1, 2 or 3, * d = 0 or 1, and * c + d lower or equal to 3, * the substituents R are as defined above in the grounds (I) and (II). According to the Applicant's knowledge, no prior art document describes polyorganosiloxanes having, at the same time, functionalized motifs by a functional moiety attached to the silica by means of a SiOC bond and siloxy functionalized motifs by a moiety attached to the silica by of a SiC link. In the polyorganosiloxane according to the invention, the first Y-alkoxy functionality is carried by the reasons of formula (I), while the second hydrocarbon functionality W appears in the motifs of formula (II) as defined above. In relation to W, the particular case in which that radical corresponds to hydrogen is that which illustrates the polyorganosiloxane which is a precursor of the multifunctional polyorganosiloxane and which constitutes another object of the invention. According to a usual terminology in silicones, those motifs (I) and (II) can be motifs M, D but also T. The presence of T-motifs corresponds to a variant in which the polyorganosiloxanes are present in the form of linear chains cross-linked between yes. The Y functions are characterized in that they are hydrolysable and that therefore they can allow the grafting on different supports, which can be particularly interesting in certain applications, that is to say ... anti-adhesion, lubrication, ... W can be constituted by a hydrocarbon function, more difficult to hydrolyze and can express various properties depending on their chemical nature. This may be the possibility of compatibility with organic polymers, or then also the contribution of a crosslinking function to the polyorganosiloxane.

According to an advantageous embodiment of the invention, this functional substituent W is selected from the following radicals: a linear alkyl alpha radical having from 8 to 12 carbon atoms, in particular radicals with halogenated functional residues [type (i)] and of formula (1) or (2): (1) (2) - a radical with a halogenated [type (i)] and etherified functional radical [type (2i)] and of formula (3): -CH- -CK-y- -CH- -CF (3: - a (poly) esterified radical of the type (2i) and of the formula (4): - CHrCH. CH. O CH, O • CH, CH (CHj) - H (ouCHj). - JT -CH- -CH- -CH- -CH- (5) - a radical of type (3i) and of formula (6), (7), (8) or (9): (6) (7) • (CH,), -o -CH, -C (8) (9) - an aryloxyalkyl radical of type (4i) and of formula (10), (11) or (12): (10) (11) - an esterified alkyl radical of type (5i and of formula (13), (14), (15) or (16): -CH CH, - -CH- -C0 CH, (14) -CH «-CH- -CH- -co C2H5 (15) or - (CH 2> 10" -C0- -CH- (16) a radical of type (6i) and of formula (17) or (18) (17) (18) a radical of type (7i) and of formula (19) or (20) -CH2 Si (OCH3) 3 (19) -CH2 CH2 YES (OC2H5) 3 (20) As indicated above, the invention is not limited to the case where the polyorganosiloxane comprises only two types of functionalities Y and W. In fact, according to an interesting variant, the polyorganosiloxane comprises, in addition to the motifs (I) and (II), at least one reason (III). These (III) SiH motifs, for example, are residual siloxyl sites whose hydrogen has not reacted to be replaced by Y or W. This residual hydrogenated character may be useful in certain applications of the polyorganosiloxanes according to the invention. It should be emphasized that, as soon as a pattern of a given type (I, II or III) is present in the polyorganosiloxane to more than one specimen, the different specimens may be identical or different from each other. Taking into account the values that can be taken by the aad indices attributed to the substituents in the motifs (I), (II), (III), it should be understood that the polyorganosiloxanes according to the invention can have a linear and / or branched structure cyclical Preferred R radicals are: methyl, ethyl, n-propyl, isopropyl or n-butyl, preferably methyl. More preferably also, at least 80% in number of R radicals are methyl. The preferred Y-alkoxy radicals are ethoxyls. To be even more precise about the polyorganosiloxanes of the invention as new products, those formed by linear, sequential or block linear copolymers of the following average formula (IV) are mentioned first: (IV) in which: - the symbols Y, W and R are as defined in the preceding, the symbol Z is a monovalent radical selected from the radicals formed by hydrogen and between those with the definitions of R, Y and W. - the indices m, n, p & q represent integers or positive decimals, and - the sum m + n + p + q is greater than or equal to 3, preferably between 3 and 100; the case of a figure in which p = q = 0, m greater than or equal to 1 and n less than or equal to 50, are particularly preferred. - 0 less than or equal to less than or equal to 100, preferably 1 less than or equal to less than or equal to 50. - 0 less than or equal to less than or equal to 100, preferably less than or equal to less than or equal to 50. - 0 less than or equal to p less than or equal to 20, preferably 0 less than or equal to p less than or equal to . - 0 less than or equal to q less than or equal to 40, preferably 0 less than or equal to q less than or equal to 20. - with the conditions according to which: if m = 0, at least one of the substituents Z corresponds to a radical of definition that characterizes Y, if n = 0, at least one of the substituents Z corresponds to a defining radical that characterizes,. and if m = n = 0, & p + q is greater than or equal to 1, then one of the substituents Z corresponds to a defining radical that characterizes Y, - and the other of the substituents Z corresponds to the definition that characterizes W; Among the polyorganosiloxanes of formula (IV), which are more particularly preferred, mention may be made of those for which p = q = 0 and 0.1 less than or equal to m / n less than or equal to 5, preferably less than or less than m / n or less. equal to 5 and more preferred still, 1.5 less than or equal to m / n less than or equal to 3. An alternative to the linear structure of the polymers of formula (IV) defined above, relates to polyorganosiloxanes consisting of cyclic copolymers of the following average formula (V): (V) in which: Y, W and R are defined as in the preceding, and with r, s, t & u that represent integers or positive decimals; + the sum r + s + t + u greater than or equal to 3, preferably comprised between 3 and 8; the case of a figure in which t = u = 0 is more particularly preferred. + 1 less than or equal to r less than or equal to 8, preferably 1 less than or equal to r less than or equal to 4, + 1 less than or equal to s less than or equal to 8, preferably less than or equal to s less than or equal to 4, + 0 less than or equal to t less than or equal to 8, preferably 0 less than or equal to t less than or equal to 4, + 0 less than or equal to u less than or equal to 8, preferably 0 less than or equal to u less than or equal to 4, Preferably, the polyorganosiloxanes according to the invention are constituted by products corresponding to those for which R = CH 3 and p = u = 0 in the formulas (IV) and (V) defined above. Of course, in those formulas (IV) and (V), as already indicated above, the radicals W may be identical or different in nature when n > 1 and s > 1.

Mixtures of polyorganosiloxanes of the type defined above are within the scope of the present invention. According to another of its aspects, this invention has as its object a process for preparing functionalized polyorganosiloxanes, in particular multifunctionalized, which may especially be those described in the foregoing. Advantageously, this functionalisation procedure essentially consists of reacting:. a starting polyorganosiloxane of motifs of formula (II) as defined above, in which W represents hydrogen, with at least one alcohol from which the functionality Y of the motif (I) derives, and which is useful at the same time as reactive and as a reaction solvent, in the presence of a catalyst from which at least one of the active elements is selected from the transition metals, according to a mechanism of dehydrogen condensation (first phase). One of the originalities of this process lies in the use of the alcohol corresponding to the group Y, both as a reactant and as a reaction solvent in the dehydrogencondensation stage. This is one of the essential differences with the method of alcoholysis known according to KOAMA and HUMEKI. In accordance with the invention, it could be noted that, whatever the amount of alcohol used in the process, it is not possible to transform all the functions siw with W = H of the starting polyorganosiloxane. In this way, after a certain limit conversion rate, which varies according to the reaction conditions, the stereometry and the nature of the reactants, the residual SiH become inactive in relation to the dehydrogencondensation. For example, in the presence of ethanol, the rate of transformation of the initial SiH functions is maintained and does not exceed a level of 66%. This original dehydrogenocondensation leads therefore to a polyorganosiloxane which comprises at least a related functionality and free SiH functions. Here, it is a precursor or an intermediary product that constitutes by itself and as such, a new product per se according to the invention. This precursor or intermediate product will allow access to the multifunctional polyorganosiloxane whose production will be detailed below. Advantageously, the starting polyorganosiloxane is selected from those of the following average formula (VI): Z'- • -z- (SAW) in which: - the symbols R are identical or different and are as defined in the legend of the formula of the motifs (I) and (II), - the symbols Z 'are identical or different and correspond to R or hydrogen , - p has the same definition as that given above in the legend of formula (IV), - v = m + n + q, with the condition that if v = 0, then p is greater than or equal to 1, and the two radicals Z 'correspond to hydrogen. The starting polyorganohydrogensiloxanes which serve, for example, to prepare cyclic functionalized products, are those selected from those of the following average formula (VII): (VII) in which: - the symbols R are identical or different and are defined in legend of the formula of the motifs (I) and (II), - u is of the same definition as the one given above , in legend of the formula (V), - y = r + s + t & and + u is greater than or equal to 3. In a privileged manner, the alcohols which are placed on site are linear or branched monohydroxylated alkanols (primary, secondary or tertiary, preferably primary), selected preferably from the following list: methanol, ethanol, (iso) propanol, n-butanol, with ethanol being preferred. In relation to the catalyst, it is advantageously selected from those which contain at least one of the following elements: Pt, Rh, Ru, Pd, Ni and their associations; that catalyst is optionally coupled with an inert support or not. According to a preferred embodiment of the invention, the catalyst is taken from the family of platinum catalysts traditionally used to carry out hydrosilylation reactions. These platinic catalysts are widely described in the literature. In particular, mention may be made of the complexes of platinum and of an organic product which are described in US-A-3 159 601, US-A-3 159 602, U3-A-3 220 972, and European patents EP-A-57 459, EP-188 978 and EP-A-190 530, as well as the platinum and vinylated organopolysiloxane complexes described in US-A-3 419 593, UA-S-3 715 334, US-A-3 377 432 and US-A-3 814 730. The karstedt catalyst is an example of a platinum catalyst suitable for the process according to the invention (US Pat. No. 3,775,452 Kardstedt). Nickel-based catalysts, such as Raney nickel, are a possible alternative to platinum catalysts. In the case of reaction conditions, the dehydrogenase condensation can be carried out over a wide range of temperature ranging, for example, from 0 ° C to 200 ° C, but it is clear that it is preferred that it be carried out at a temperature comprised between 20 ° C and 80 ° C. ° C, preferably between 40 ° C and 70 ° C. The second phase of the process according to the invention consists in preparing a multi-functionalized polyorganosiloxane from the precursor or intermediate polyorganosiloxane, produced by dehydrogencondensation as explained above.

To do this, the polyorganosiloxane transformed by dehydrogencondensation is reacted with at least one olefinic compound carrying at least one Pi bond, so as to allow the addition of the polyorganosiloxane transformed on that olefinic compound according to a hydrosilylation mechanism, in the presence of a catalyst, and preferably at a temperature between 5 ° C and 100 ° C and still more preferably between 20 ° C and 90 ° C. Therefore, this hydrosilylation proceeds to the dehydrogen condensation. initiates hydrosilylation by adding the olefinic compound from which the radical as defined above derives, to the intermediate alkoxylated polyorganosiloxane once the dehydrogencondensation is terminated.In practice, this addition can be done when the evolution of hydrogen has ceased. be formed by a mixture of products comprising a to single or several precursors of radicals W, which determine the multifunctionality of the final polyorganosiloxane. In the case where several W species are provided, it is preferably left to react first the alcene corresponding to the second functionality, and then once it has reacted completely, the alcein corresponding to the third functionality is incorporated and thus in ahead. Instead of being incorporated into the reaction medium after the dehydrogencondensation, the precursor olefinic compound of W can be put into operation before this first stage of the process begins, or then also during it. According to a preferred feature of the invention, it is acted in such a way that the hydrosilylation is catalyzed by at least a part of the dehydrogencondensation catalyst and, preferably, exclusively by that catalyst. This is one of the particularly interesting and unexpected points of the method of the invention. Indeed, it is totally surprising to note that the dehydrogencondensation catalyst, preferably of the platinic nature, is always active for this second hydrosilylation phase. In fact, it is well known that the catalyst undergoes a certain impoverishment of its behavior at the time of dehydrocondensation. But what is still astonishing is that the catalyst is present in the medium containing the polyorganosiloxanes carrying SiH residual post-dehydrocondensation. In theory and according to a widely distributed prejudice in the field under consideration, the hydrosilylation catalyst, particularly platinum, is active only if it is first placed in the presence of the reactive product comprising at least one Pi bond. In such a way that the formation of an inactive colloid should have been observed in the case of the invention, but that does not happen. On the contrary, the residual SiHs are particularly reactive in relation to the added olefinic compounds thanks to the action of the hydrosilylation catalyst, which is also fully effective. This result makes it possible to obtain, in a single sequence and without changing the reactor, a polyorganosiloxane comprising several different functionalities. The olefinic compounds that are put into work can easily be deduced from the definition of W given in the above. The selection in regard to that radical, is determined by the applications that are tried to obtain (one or several different functionalities). The hydrosilylation phase can advantageously be carried out at ambient temperature and in bulk or in solution, for example in the alcohol which served as the solvent and as a reagent in the dehydrogen condensation reaction. At the end of the reactions, the obtained crude oleoorganosiloxanes can be purified mainly by passing over a column filled with ion-exchange resin and / or by simple devolatilization of the reactants that were introduced in excess and optionally of the solvent that is put into work, by heating operated between 100 ° ^ and 180 ° C under reduced pressure. According to another of its aspects, the present invention relates to the application of the polyorganosiloxanes defined above, as well as those obtained by the method also described in the foregoing, as anti-adhesion modulators and / or of crosslinking agents in silicone compositions or also as a mineral filler such as silica, carbonates, carbon black, etc ... In particular, these polyorganosiloxanes can be used as additives for surface treatment compositions, in particular paper, concrete, metal, etc ... These compositions can advantageously be varnishes, paints, non-stick coatings, etc ...

The subject of the present invention is also, for example, the silicates comprising the polyorganosiloxanes described above, as active ingredients. To be more precise, we can mention: - non-stick compositions for paper, - lubricant compositions, compositions containing organic polymers and polyorganosiloxanes which are considered to be provided with functionalities that are compatible. The present invention will be better understood in the light of the following examples which describe the different multifunctional polyorganosiloxanes as well as their preparation process. Other advantages and variants of putting into work of the invention, will also be evident with these examples.

E J E M P L O S I - First phase of the method according to the invention. Example 1: Preparation of a first polyoraanosiloxane (POS) of functionalities SiOEt v SiH = precursor of multifunctional POS that is obtained by dehydroseno-condensation: In a 500 ml three-neck flask equipped with mechanical stirring, with a thermometer, and with one pouring blister, 200 ml of ethanol previously dried on 3 Angstrom molecular sieve, and 10 μl of KARDSTEDT catalyst (10% in hexane) are charged under a nitrogen atmosphere. The mixture is stirred at 65 ° C and the polymethylhydrosiloxane (40 g, dpn = 50) is added dropwise. A significant hydrogen evolution is observed. The casting speed of the Si-H fluid is regulated to control the flow rate of the hydrogen and the exotherm of the reaction. At the end of the wash, the mixture is left for one hour under agitation. The excess ethanol is removed with the aid of a rotary evaporator. 59.5 g of a clear and colorless oil, with a viscosity of 52 mPa.s, is recovered, which corresponds to the average formula below, after an NMR analysis: This oil has a very good storage stability protected from moisture.

Example 2: Preparation of a second POS precursor of Si-OEt v Si-H: The reagents and the protocol are the same as in example 1. The product obtained is of the same formula with the small difference that m = 32 and n = 18.

Example 3: Preparation of a third functional POS Si-OiPr v Si-H: Proceed as in example 1, but replacing the ethanol with isopropanol (iPr). 52.2 g of an oil corresponding to the following average formula (NMR) are obtained: II. First and second phases of the method according to the invention: Example 4: Preparation of a POS of Si-OEt functionalities v Si-EPOXI. The procedure is as in Example 1, but instead of evaporating the excess alcohol, 35.3 g of vinylcyclohexene oxide (1.5 eq / SiH) are added dropwise. After the addition, the reaction mixture is heated to 60 ° C until all the SiH functions are finished. Then, excess alcohol and vinyl cyclohexene oxide evaporates. 81 g of limpid and slightly colored oil are recovered. The NMR analysis reveals the following structure (NMR): It is noteworthy that in the course of this reaction no openings of epoxy functions are observed by the SiH functions. Example 5: Preparation of a POS functionality Si-OEt v Si-EPOXI. The reagents and the protocol are identical to those of example 4. The POS has the same formula with the small difference that = 32, n = 18.

Example 6: Preparation of a POS of Si-OEt functionalities v Si-methylbutyl fluorohexane. The procedure is as in Example 4, replacing the vinylcyclohexene oxide with the following two co -omers: CH. C "FlT-CH. CH = C (80%) \ CH, Vp CH, -CH, -C = CH (20%) CH, The amounts of POS SiOET / SiH and co -omers that are put into work, are respectively 25 g and 153 g.

The temperature of the reaction medium is maintained at about 70 ° C. 49.09 g of POS SiOEt / Si-fluoroalkyl of formula are recovered: Example 7: Preparation of a POS of Si-OEt functionalities v Si-methylpropyl chloride. The procedure is as in Example 4, but replacing the vinylcyclohexene oxide with methallyl chloride. The quantities of reagent that are put in place are the following: - POS SiOEt / SiH = 100 g - Metalyl chloride = 32.78 g - [Pt] Initial Karstedt = 14 mg The temperature of the reaction medium is maintained at 25 ° C - 30 ° C approximately. 101.51 g of a clear colored oil are recovered, decolorable on Ambersys H21 resin. The NMR reveals the following formula: Example 8: Preparation of a POS of Si-OEt functionalities. Si-octyl v Si-EPOXI. 8.1.- Synthesis: Proceed as in example 4, with the small difference that is part of POS: SiOiPr / SiH of formula: Me.Si-O > The reagents that are put in place, are: + POS SiOPr / SiH = 78.3 g + octene-1 = 16.4 g + vinylcyclohexene oxide (VCHO) = 18.8 g > Operative mode: The octene is first added on a foot of POS and [Pr] Kardetedt in isopropyl alcohol, Temperature = 25 ° C - 30 ° C approximately. The reaction is left until a part of SiH is consumed (30 minutes). . It is heated to 70 ° C to evaporate the alcohol and octene in excess.

. The VCH is added. Temperature = 25 ° C. This reaction temperature is maintained until the complete consumption of SiH. . It is heated to 70 ° C to remove the reactive excess. A slightly colored limpid oil of formula is recovered: 8. 2.- Application: The UV reactivity of the trifunctional POS that was obtained is measured in the presence of 0.3% of photoprugipifier constituted by a 20% by weight solution in isopropyl alcohol of tetrakis- (pentafluorophenyl) -borate of ditholuiliodonium. This measurement is made with the aid of a VNC gel point measuring device [Vibrating needle curemeter] marketed by the RAPRA Ltd. Company, to which a UV irradiation device was added.

In the course of the crosslinking, the needle of the VNC submerged in the mixture to be studied, will find a resistance that will be manifested by a decrease in the output voltage of the device. The time required to reach a decrease in the output voltage of the apparatus is measured, namely: 10.50 and 90% decrease in tension, for a thickness to be polymerized of 2 mm. The attached figure 1 illustrates the RAPRA curve that was obtained. You can read it: UNCLE = 1.3 minutes T80 = 1.8 minutes T95 = 2.4 minutes T100 = 3.8 minutes VIO = 91.9 V V95 = 12.1 mV These results are completely correct for a non-stick paper coating application.

Example 9: Preparation of a POS of Si-OEt functionalities. Si-octyl v Si-tMel • > The reagents that are put in work, are the following: POS Si- (Me) 2 of formula: Quantity: 100 g - EtOH = 500 g - Platinum (Karstedt to 13.6%) = 20 pp / oil, be 14.7 mg - octene-1 = 29.12 g - VCHO (vinylcyclohexene oxide = 14.28 g> Operating procedure: + Charge ethanol and Pt in a 2-liter four-necked flask, + Sink then the POS for 2 hours and then the octene, + heat to 60 ° C for one hour, + then pour the VCHO in excess, + is heated to 70 ° C by adding a few drops of [Pt] and the reaction is maintained until the complete consumption of the SiH. + is allowed to cool, + an oil is recovered whose NMR analysis gives the following formula: Me-Si 04- 0- SiMe L 50 Example 10: Preparation of a POS of Si-OEt functionalities. Si-octyl v Si-EPOXI. > The reagents that are put in work, are the following: POS Si-H of formula: = • 240 g EtOH = 1000 g [Pt]. { Karstedt 13.6%) = 32.5 mg octene = 69.0 g VCHO = 70.0 g - > Operative mode: - It is charged in a 2-liter three-necked flask, ethanol, platinum and POS SiH, - initially the temperature of the reaction medium is room temperature, - Slowly (3 hours) the POS is introduced over the alcohol and the Pt, - according to the casting, the temperature is raised to approximately 40 ° C and then maintained at this value during the essential part of the reaction, - at the end of the casting, the stirring is maintained for several hours, then the progressively octene; temperature at 20 ° C-40 ° C approximately, finally, then the VCHO is incorporated; temperature at about 40 ° C, - it is heated to 70 ° C to eliminate the excess of reagents, a lightly colored limpid oil is recovered whose NMR analysis gives the formula:

Claims

R E I V I N D I C A C I O N S

1. - Functionalized polyorganosiloxane, comprising, per molecule: alpha.- on the one hand, at least one siloxyl functional motif of the formula: (I) (R), Y Yes (0) 3 - a wherein: * a = 0, 1 or 2 * R is a monovalent hydrocarbon radical selected from straight or branched alkyls having from 1 to 6 atoms in particular methyl, ethyl, propyl, butyl and / or aryls and in particular phenyl, methyl which are more particularly preferred; the radicals R are identical or different when a = 2. * Y is a linear or branched alkoxy radical selected, preferably, from the alkoxyls in C ^ _ C15, in particular? ~ C6 'methoxy, ethoxy and (iso) propoxy are more particularly preferred. beta.- and, on the other hand, at least one functional siloxyl motif of the formula: (II) (R) b W Si (0) 3 _ b 2 in which: * b = O, 1 or 2, * R has the same definition as that given above for the substituent R of the motive (I) and may be identical or different from the latter. * is hydrogen or a monovalent hydrocarbon radical having from 2 to 30 carbon atoms and optionally S and / or O atoms and / or halogens and constituting a functional moiety, linked to the silica by a Si-C bond; this residue is selected from the following groups: (i) an alkyl, aralkyl or aryl group substituted by one or more halogen atoms (s) and / or by a mono- or poly-halogenoalkyl radical, (2i) a polyether group oxide of formula (R 1 O) e R 2 with R 1 representing an alkylene group, and R 2 representing a hydrogen atom or an alkyl group and e = 1 to 5, (3i) an epoxy group resulting from the attachment of an oxygen with two carbon atoms belonging to a cycloalkyl or alkenyl alkyl group, (4i) an alkoxyalkyl or aryloxyalkyl group, (5i) a mono- or poly-hydroxylated and / or mono- or poly-carbonyl and / or mono alkyl group - or poly-esterified, (6i) a sterically hidden phenolic group or a group derived from a mono- or di-hydroxylated benzophenone, (7i) an alkoxysilyl group, preferably trialkoxysilyl; the bda - and possibly at least one reason (III) of the following formula: (R) c (H) d Si (Q) 4. (c + d) (III) 2 in which: * c = 0, 1, 2 or 3, * d = 0 or 1, and * c + d less than or equal to 3, * the substituents R are such as defined above in the reasons (I) and (II).

2. Polyorganosiloxane according to claim 1, characterized in that the substituent W different from H of the motif (II), is selected from the following radicals: an alpha linear alkyl radical having from 8 to 12 carbon atoms, in particular radicals with halogenated functional residues [type (i)] and of formula (1) or (2): (1) (2) - a radical with a halogenated functional moiety [type (i)] and etherified [type (2i)] and of formula (3): -CH- -CH- -CH, -CF (3) - a (poly) esterified radical of the type (2i) and of the formula (4): - CHrCH. -CH, (CH,), (• ») -CH- -CH- -CH- -O- -CH- 5) - a radical of type (3i) and of formula (6), (7), (8) or (9): (6) (7) • (CH,) 3 -O-CH, -CH-CH. ou - (CH,), - O-CH-CH, \ / \ / 2 O O (8) (9) - an aryloxyalkyl radical of type (4i) and of formula (19, (11) or (12): CH, -CH, -CH: -0? Q; _CH: _CH_0? Q. (10) (11) -CHrCH, -CH, (12) - an esterified alkyl radical of type (5 ±; formula (13), (14), (15) or (16): - (CH2) 3 OH (13) -CH- -CH- -CH '-O- -co CH- (14) -CH '-CH - -CH' -O- -CO C2H5 (15) - (CH2) 10 CO OR CH3 (16) - a radical of type (6i) and of formula (17) or ' (17) (18) - a radical of type (7i) and of formula (19) or (20) -CH2 Yes (OCH3) 3 19) or -CH2 CH2 YES (OC2H5) 3 (20)

3. - Polyorganosiloxane according to claim 1, characterized in that it is formed by a linear, statistically, sequenced or block copolymer of the following average formula (IV):

(IV) wherein: - the symbols Y, W and R are as defined in claims 1 and 2, - the symbol Z is a monovalent radical selected from the radicals formed by hydrogen and between those with the definitions of R, Y and W, - the indices m, n, p &; q represent integers or positive decimals, and - the sum m + n + p + q is greater than or equal to 3, preferably between 3 and 100; the case of a figure in which p = q = 0, greater than or equal to l and n less than or equal to 50, are particularly preferred. - 0 less than or equal to less than or equal to 100, preferably 1 less than or equal to less than or equal to 50. - 0 less than or equal to less than or equal to 100, preferably less than or equal to less than or equal to 50. - 0 less than or equal to p less than or equal to 20, preferably 0 less than or equal to p less than or equal to 10 - 0 less than or equal to q less than or equal to 40, preferably 0 less than or equal to q less than or equal to 20. - with the conditions according to which: if m = 0, at least one of the substituents Z corresponds to a defining radical characterizing Y, if n = 0, at least one of the substituents Z corresponds to a defining radical that characterizes W, . and if = n = 0, & p + q is greater than or equal to 1, then one of the substituents Z corresponds to a defining radical that characterizes Y, - and the other of the substituents Z corresponds to the definition characterizing W; 4. Polyorganosiloxane according to claim 3, characterized in that p = q = 0 and 0.1 less than or equal to m / n less than or equal to 5, preferably 1 less than or equal to m / n less than or equal to 5, preferably 1 less than or equal to m / n less than or equal to 5 in formula (IV). 5. Polyorganosiloxane according to clause 1 or 2, characterized in that it is constituted by a cyclic copolymer of the following average formula (V):

(V) wherein: Y, W and R are defined as in claims 1 and 2, and with r, s, t & u that represent integers or positive decimals; • * - the sum r + s + + u greater than or equal to 3, preferably between 3 and 8; the figure case in which t = u = 0 is more particularly preferred, + 1 less than or equal to less than or equal to 8, preferably 1 less than or equal to less than or equal to 4, + 1 less than or equal to less than or equal to 8, preferably 1 lower or equal to less than or equal to 4, + 0 less than or equal to t less than or equal to 8, preferably 0 less than or equal to t less than or equal to 4, + 0 less than or equal to or less than or equal to 8, preferably 0 less than or equal to or less than or equal to 4,

6. - Polyorganosiloxane according to claim 3, 4 or 5, characterized in that it comprises products corresponding to those for which R = CH3 and p = u = 0 in the formulas (IV) and (V).

7. Polyorganosiloxane formed by a polyorganosiloxane mixture according to any of claims 1 to 6.

8. Process for preparing a polyorganosiloxane and especially that according to any of claims 1 to 8, characterized in that it consists essentially in making reacting: a starting polyorganosiloxane comprising motifs of formula (II) as defined in claim 1, and in which W represents hydrogen, with at least one alcohol from which the functionality Y of the motif (I) derives, and it is useful both as a reactant and as a reaction solvent, in the presence of a catalyst from which at least one of the active elements is selected from the transition metals, according to a mechanism of dehydrogencondensation (first phase).

9. Process according to claim 8, characterized in that the starting polyorganosiloxane is selected from those of the following average formula (VI): (SAW) in which: - the symbols R are identical or different and are as defined in the legend of the formula of the motifs (I) and (II), according to claim 1, - the symbols Z 'are identical or different and correspond R to hydrogen, - p has the same definition as that given above in the legend of formula (IV), according to claim 3, - v = m + n + q, with the condition according to which if v = 0, then p is greater than or equal to 1, and the two radicals Z 'correspond to hydrogen.

10. Process according to claim 9, characterized in that the polyorganosiloxane is selected from those of the following average formula (VII): (VII) wherein: - the symbols R are identical or different and are defined in legend of the formula of the motifs (I) and (II), according to claim 1. - u is of the same definition as the one given above, in legend of the formula (V), according to claim 5. - y = r + s + t & and + u is greater than or equal to 3.

11. Process according to any of claims 8 to 10, characterized in that the alcohol is selected from the following list: methanol, ethanol, (iso) propanol, (n) butanol, Ethanol is preferred.

12. Method according to any of claims 8 to 11, characterized in that the catalyst is selected from those that contain at least one of the following elements: Pt, Rh, Pd, Ni and their associations (platinum is particularly preferred), whose catalyst is optionally coupled to an inert support or not.

13. Process according to any of claims 8 to 12, characterized in that the dehydrogen condensation is carried out at a temperature comprised between 20 ° C and 80 ° C. preferably between 40 ° C and 70 ° C.

14. Process according to any of claims 8 to 13, characterized in that the polyorganosiloxane transformed by dehydrogencondensation, is reacted with at least one olefinic compound carrying at least one Pi bond, so as to allow the addition of the first on the second, according to a hydrosilylation mechanism, in the presence of a catalyst and, preferably, at a temperature comprised between 5 ° C and 100 ° C, and even more preferred, between 20 ° C and 90 ° C.

15. Process according to claim 14, characterized in that the olefinic compound is added to the reaction medium, before, during or after the dehydrogencondensation.

16. Process according to claim 14 or claim 15, characterized in that it is done in such a way that the hydrosilylation is catalyzed by at least a part of the dehydrogen-condensation catalyst and, preferably, exclusively by that catalyst.

17. Application of the polyorganosiloxanes obtained according to any of claims 1 to 7, and / or of the polyorganosiloxanes obtained by the process according to any of claims 8 to 16, as anti-adhesion modulators in silicone compositions. .

18. Application of the polyorganosiloxanes according to any of claims 1 to 7, and / or of the polyorganosiloxanes which are obtained by the process according to any of claims 8 to 16, as additives for surface treatment compositions, in particular of paper, concrete, metal, etc ...; Advantageously, these compositions are varnishes, paints, non-stick coatings. 70 75 twenty 25 RE S UME N The present invention relates to multifunctional polyorganosiloxanes comprising per molecule, on the one hand, at least one functional siloxyl (I): (R) to Y Si (0) (3_a) 2 / where R is primarily a radical alkyl in C? -C-6, Y is an alkoxy radical in CÍ-CJS and a = 0, 1 or 2; ß on the other hand, at least one other functional siloxyl (II) motif: (R) b W Si (0) 3_b) 2 wherein W is hydrogen or a group attached to the silica by a Si-C bond, selected from the groups: alkyl, aralkyl or halogenated or polyhalogenated aryl; polyether oxide; epoxidized alkyl, alkoxy alkyl; hydroxylated, carbonyl or esterified alkyl; phenolic and alkoxysilyl; ? and optionally at least one motif (III): (R) c (H) dSi (0) [(4_ (0 + d)] 2 where C = 0, 1, 2 or 3, d = 0 or l and c + d is < 3. The alkoxy functionality Y is introduced on an appropriate polyhydrogen-organosiloxane by a dehydrogen condensation reaction from the alcohol from which Y is derived, and then the functionality by a hydrosilylation reaction from the olefinic compound from which it derives. Multifunctional polyorganosiloxanes can be used as anti-adhesion modulators in the silicone compositions.