EP1149123A1

EP1149123A1 - Peroxidised polyorganosiloxanes (pos), one of the methods for preparing them and their uses as bleaching agent in dental compositions

Info

Publication number: EP1149123A1
Application number: EP99973300A
Authority: EP
Inventors: Adrien Dromard; Gérard Mignani; Lucile Gambut; Frédéric DALLEMER
Original assignee: Rhodia Chimie SAS
Current assignee: Rhodia Chimie SAS
Priority date: 1998-12-09
Filing date: 1999-12-01
Publication date: 2001-10-31
Anticipated expiration: 2019-12-01
Also published as: US20050003995A1; FR2787114A1; EP1149123B1; DE69917942D1; US6841645B1; AU1393300A; WO2000034360A1; DE69917942T2; ATE268793T1; FR2787114B1; ES2223196T3

Abstract

The invention concerns polyorganosiloxanes (POS) grafted with peroxide functions and functions stabilizing the latter. Said stabilized peroxidised POS are designed to form a novel oxidizing system useful as bleaching agents, for example or dental or detergent compositions. The invention aims at and succeeds in providing peroxygenated bleaching agents more stable and more efficient than those known in prior art. The inventive stabilized and peroxidised POS correspond for example to the formula (a). The invention also concerns a method for making said peroxidised POS, the precursors thereof and their uses as bleaching agents in dental compositions (toothpaste or detergent compositions).

Description

POLYORGANOSILOXANES (POS) PEROXIDES, ONE OF THEIR PREPARATION METHODS AND THEIR USES IN PARTICULAR AS A WHITENING AGENT IN DENTAKE COMPOSITIONS The field of the invention is that of peroxide systems applicable in particular in bleaching, disinfection, cleaning, initiation of polymerizations (for example radical) or epoxidation reactions. The oxidizing properties of these systems are more particularly appreciated in bleaching applications, in particular dental (e.g. toothpaste) or detergent. The peroxide systems referred to in the context of this presentation are functionalized polymers.

The present invention relates to polyorganosiloxanes (POS) peroxides as well as one of their methods of preparation.

The invention also relates to silicone precursors of these peroxide POSs.

Finally, the present invention includes an application aspect which includes the use of the peroxide POSs according to the invention as active ingredient in bleaching, disinfection, cleaning and initiation of chemical reactions. More specifically, the invention relates to dental compositions, for example toothpastes, or detergents comprising POS peroxides as a bleaching agent.

It is known in the field of whitening, in particular dental whitening, to use hydrogen peroxide H ₂ O ₂ or its persalts (percarbonates, perborates, calcium peroxides). In the remainder of this description, H ₂ O _{2 will} designate H ₂ O ₂ as such and its persalts. The disadvantages of hydrogen peroxide are not negligible. First, H ₂ O ₂ must be used in high concentration to be effective. This point is particularly troublesome given the aggressiveness of H ₂ O ₂ . Second, we know that the bleaching action is linked to the oxygen-giving effect. However, this effect is not the predominant effect that can be obtained with hydrogen peroxide. The latter behaves essentially as a promoter of deleterious free radicals, which do not participate in the bleaching function and which would even rather tend to thwart it. Third, hydrogen peroxide has the disadvantage of being unstable.

There is therefore a clearly identified need for a substitute for hydrogen peroxide for these applications in the field of whitening and in particular dental whitening (toothpaste).

In an attempt to solve the above-mentioned problem, peracid compounds constituted by a support have been proposed in US patent No. 5,698,326 inorganic formed by silica and carrying peracid functionalities. These compounds can be obtained by reacting silica substituted with a siloxylalkylamine residue with a trimellitic anhydride, the carboxylic function of the benzyl ring of which is then oxidized to transform it into a peracid function. This corresponds to the following formula:

O

o

According to this patent, the grafting of the peracid function on the inorganic silica support is supposed to allow stabilization of the peracid function. In reality, it turns out that this stability could be further improved. In addition, it is to be feared that these peroxidized silicas are difficult to disperse in relatively viscous compositions such as toothpaste.

European patent application No. 796 874 relates to a process for the preparation of polymers comprising peroxycarboxylic groups. These peroxycarboxylic polymers are more precisely copolymers of N-vinylpyrolidone / maleic anhydride. The hydrogen peroxide which is reacted with this copolymer allows the conversion of the carboxyls obtained from the anhydride into peroxycarboxylic functions. The performance of these peroxycarboxylated copolymers, in terms of bleaching, is not revealed by this patent application. Furthermore, it seems that in the teeth whitening application, the peroxycarboxylated copolymers lack selectivity with respect to the teeth. In addition, instability problems can be feared for dental bleaching applications of these copolymers.

PCT patent application WO 97/02 01 1 discloses dental oral compositions comprising conventional ingredients such as abrasives, binders, humectants, surfactants, sources of fluorine ions or other sweeteners, as well as two other essential ingredients namely, on the one hand, an aminoalkylsilicone such as a polydimethylsiloxane comprising aminoalkyl units of the propylaminoethylamine type in the chains and at their ends and, on the other hand, a polydimethylsiloxane comprising pendant groups of polyoxyethylene type and / or polyoxypropylene and having a surfactant action. There is no question in this document of polyorganosiloxanes functionalized with peroxide units. This oral composition is presented as having improved anti-plaque and anti-bacterial properties, which complement excellent cleaning performance. This oral composition can also include bleaching agents belonging to the family of inorganic peracid salts (persulfates, perborates, percarbonates and metal peroxides). These oral compositions are not satisfactory in terms of stability, toxicity, selectivity with respect to the teeth and efficacy of bleaching by oxidation.

In such a state of the art, one of the essential objectives of the inventors was to develop a new oxidizing system which can be used in particular in bleaching, for example dental or washing powder, in disinfection, in cleaning or in the initiation of chemical reactions, this peroxide-type oxidizing system must be more stable and more effective than the known systems of the prior art.

Another essential objective of the invention is to provide a peroxide whitening system in particular for dental whitening applications which makes it possible to control the reactivity of the peroxide function, so as to limit as far as possible its transformation into aggressive free radicals.

Another essential objective of the invention is to provide a peroxide whitening system usable in particular in dental whitening and endowed with significantly improved storage stability.

Another essential objective of the invention is to provide a peroxide whitening system applied in dental whitening (oral composition for the treatment and maintenance of teeth), having better selectivity with respect to the teeth to be whitened. Another essential objective of the invention is to provide an oxidizing peroxide system, capable of being used as a system for controlled release of oxidizing peroxide functions, or even of free radicals initiating chemical reactions.

Another essential objective of the invention is to provide a process for obtaining the above-mentioned peroxide oxidizing system, which is simple to implement and economical.

Another essential objective of the invention is to prescribe the use of the above-mentioned peroxide oxidizing system, as a bleaching agent, a disinfecting agent, a cleaning agent or an agent for initiating reactions. chemicals. Another essential objective of the invention is to provide a dental composition provided with an effective, stable and selective whitening agent. Another essential objective of the invention is to provide a washing composition comprising an efficient, stable and economical bleaching agent.

These objectives, among others, are achieved by the present invention which relates to new polyorganosiloxanes (POS) comprising siloxane units of formula (I) below:

R _n Eb _h Gc SiO 4. - (, a _ +, b_ + c).

00 ²

-" in which :

D a + b + c = 0 to 3 D a, b, c - 0 to 3 DR corresponds to one or more identical or different radicals, R being chosen from hydro-carbon monovalent groups, preferably from linear, branched alkyls and / or cyclic and / or aryls, and more preferably still among linear or branched C1-C4 alkyls and phenyl, xylyl and tolyl groups;

DE corresponds to one or more identical or different functional substituents between them monovalent, carrying one or more peroxo (-OO-) Fpo functions and optionally each comprising one or more Fstab stabilizing Fpo functions, identical or different between themselves and chosen from functions capable of binding via weak links with Fpo functions;

D G corresponds to one or more identical or different functional substituents with one another and each comprising one or more Fstab stabilizing functions of Fpo, identical or different from one another and chosen from the functions capable of binding via weak bonds with the Fpo functions; - ”with the conditions under which:

. (i). the concentration of functions [Fpo] expressed by the ratio number Fpo total number of silicon atoms in the POS is defined as follows:

Δ 0 <[Fpo]

Δ preferably 0.01 <[Fpo] <1.0

Δ and more preferably still 0.1 <[Fpo] <0.6. . (ii). the concentration in molar% of siloxane units T (a + b + c = 1) and / or Q (a + b + c = 0) is defined as follows: Δ 0 <[T and / or Q] <20

Δ preferably 0 <[T and / or Q] <10

Δ and more preferably still, 0 <[T and / or Q] <8.

These new peroxide POSs make it possible to stabilize the peroxo function and to control its oxidizing activity by restraining its activity of producing free radicals. In addition, their teeth whitening and selectivity properties make them particularly suitable and effective whitening systems for dental oral compositions such as toothpaste.

Indeed, these silicones functionalized with Fpo peroxo are endowed with a specific affinity with respect to the constituent materials of the teeth (in particular hydroxyapatite) so that they are selective vectors capable of carrying the bleaching functions. chemical on the teeth. It goes without saying that this optimizes the efficiency of said functions. It follows that it is possible to reduce the doses, which is entirely in the direction of reducing the aggressiveness of the bleaching agent. In addition, these peroxide functional silicones are hydrophobic and therefore have the advantage of preserving the Fpo functions of water, which is a major element of instability for these.

The new peroxidic polyorganosiloxanes with Fpo functions can be linear and / or branched and / or crosslinked polymers according to the percentage by weight of DTQ siloxyl units which they comprise. Preferably, the peroxide POSs according to the invention mainly comprise D units (a + b + c = 2) and more preferably still are linear.

Advantageously, the substituents E of the siloxane units (I) are identical, or different from one another and are chosen from hydrocarbon, (cyclo) aliphatic and / or aromatic and / or heterocyclic groups optionally comprising one or more heteroatoms - preferably O, N, S, Si-, these groups possibly being substituted,

Equally advantageously, Fpo is understood:

- C— OOX

> either in an acyl peroxide: ^ with X corresponding to H, to R ^x representing a monovalent hydrocarbon radical, that is to say comprising, inter alia, hydrogen and carbon atoms, aliphatic and / or alicyclic and / or aromatic and / or heterocyclic optionally comprising one or more heteroatoms (N, O, S ...), this radical possibly being substituted, R ^x possibly being able to answer the same definition as that given above for R in the formula (I), to a halogen preferably chlorine or to a cation allowing to form a salt with the peroxo anion and preferably chosen from among the elements of columns la and

IIA of the periodic table,

> either in a peroxide residue comprising sulfur, silicon phosphorus or boron as an oxygen carrier.

In other words, each peroxo Fpo function belongs to a peroxycarboxylic residue (acids - esters - halides - chlorides - or salts) or even a peroxide residue derived from compounds comprising sulfur, phosphorus, boron or silicon.

It can be e.g.:

with X as above

As examples of X = alkyl groups, mention may be made of: methyl, ethyl, propyl, butyl.

As examples of groups X = cations, we can cite: Na ⁺ , K ⁺ , Ca ⁺⁺ , Mg ⁺⁺ ...

These peroxycarboxylic and non-carboxylic residues are connected to the silicon of the POS chain by a hydrocarbon ball (that is to say comprising in particular carbon and hydrogen atoms), aliphatic and / or alicyclic and / or aromatic and / or heterocyclic optionally comprising one or more heteroatoms: N, O, S ..., possibly.

The set including:

On the one hand, the peroxycarboxylic residue and / or the non-carboxylic peroxy,

And on the other hand, the ball joint forms the functional substituent E. In practice, the ball joint is, for example, of the -alkyl-O-aryl (benzyl), -alkyl anhydride, -alkylimide-aryl (benzyl) type, among others.

The advantageous stabilizing action of Fstab on Fpo is a preferred characteristic of the functionalized POSs according to the invention. In accordance with the latter, the Fstabs are located on the functional (pendant) substituents E and / or G. Without this being limiting, it is preferable that the Fstabs are carried at least by the or the E, so as to be close to the Fpo to be stabilized. It is not forbidden to think that the stabilizing effect of Fstab is thus improved.

According to a preferred characteristic of the invention, the possible stabilization functions Fstab of the substituents E and / or G of formula (I) correspond to functions which can generate weak bonds (hydrogen bonds, eg) with Fpo, and selected in the group including:

-> the functional units comprising nitrogen and / or oxygen and / or fluorine, and / or sulfur and / or phosphorus; the carboxylic, carboxylate, amide, imide, sulfonamide, hydroxyl, alkoxyl, amino or organofluoric units being preferred;

- cationic units, preferably those comprising one or more quaternary ammoniums; - »chelating units comprising one or more ether functions and / or one or more amino functions, and / or phosphonate and / or sulfonate chelating units.

The optional functional substituents G each comprise, in addition to the Fstab (s), a ball joint which ensures the connection with the silicone chain.

The ball joints of the substituents G are identical or different from each other, which correspond to the same definition as that given above for the ball joints of the substituents E. The peroxide POSs which are the subject of the invention can be obtained: either from chlorosilanes or alkoxysilanes carrying the substituents E, chlorosilanes or alkoxysilanes carrying the substituents G and chlorosilanes or alkoxysilanes carrying the substituents R and / or hydrogen, by cohydrolysis, polycondensation and polymerization of the hydrolysed products in the presence of cyclic diorganosiloxanes or redistribution in the presence of polydiorganosiloxanes ... or from polydiorganosiloxanes functionalized by hydrosilylation of hydrogenated polydiorganosiloxanes using integral or partial olefinic precursors of the functional substituents

E and G.

Within the meaning of the present description, the terms "integral or partial olefin precursors" correspond respectively:

• in the event that the olefinic precursor is in final form and does not have to undergo other grafting to lead to the entirety of the substituent which will be transformed into E or G after peroxidation (integral ball joint), • and in the case where the ball joint of the substituents E or G is formed by several links placed end to end and corresponding to intermediate forms of synthesis, the olefinic precursor constituting the first link which is linked, on the one hand, to the silicone chain and, on the other hand, to the next link of the patella

Without being limiting, according to the invention, the peroxides POS obtained by hydrosilylation of olefinic precursors of substituents E and G are preferred.

These hydrosilylation reactions can be carried out at a temperature of the order of 15 to 200 ° C, preferably of the order of 20 to 100 ° C, in the presence of a catalyst based on a metal from the group of platinum Mention may in particular be made of the complex derivatives of platinum described in US Pat. Nos. 3,715,334, 3,775,452, 3,814,730, 3,159,601, 3,159,662.

The quantities of platinum catalysts used are of the order of 1 to 300 parts per million, expressed as metal relative to the reaction medium.

Advantageously, the olefinic precursors used in these hydrosilylations do not include the peroxo Fpo functions, but their non-peroxygenated forms F'po or any intermediate forms thereof. It is preferable in accordance with the invention to provide protection for the precursor functions F'po before hydrosilylation

The POS grafted by hydrosilylation and carrying the F'po precursor functions, are optionally purified and then subjected to an oxidation which allows the transformation of the F'po functions into Fpo functions

According to a preferred embodiment of the invention, the peroxide POSs correspond to the formula (H) given below in which

R ¹ , R ³ independently representing a hydrogen, a hydroxyl or a monovalent residue corresponding to the same definition as that given for R above,

R ² independently represent hydrogen, a hydroxyl or a monovalent residue corresponding to the same definition as that given for R above,

2 <m + n + o <300 preferably 3 <m + n + o <50 and more preferentially still 5 <m + n + o <20 0 <m <200 preferably 1 <m <100 and even more preferably l ≤ m ≤ 10

0 <n <50 preferably 1 <n <10 and more preferably still 2 <n <4

0 <o <50 preferably 1 <o <10 and more preferably still 2 <o <4.

Even more preferably, the polyorganosiloxanes are characterized in that:

Δ R ¹ , R ³ = all yl in Cι-C, preferably - CH ₃ Δ R ² = alkyl in Cι-C ₃ , preferably - CH

Δ the functional substituent (s) E, comprise both Fpo and Fstab functions. In practice, without this being limiting, the functional substituents E of the peroxide POSs each comprise a ball joint comprising at least one bicarboxylated and / or benzoxylated and / or imide unit.

The case where the ball joint (s) of the functional substituent (s) E comprise at least one bicarboxylic unit, corresponds to a preferred form of the invention in which the Fpo function is obtained from an anhydride which is transformed, on the one hand , in Fpo and, on the other hand, in a carboxylic Fstab function for stabilizing the neighboring Fpo.

The peroxide POSs according to the invention are stable and have a strong whitening power.

According to another of its aspects, the present invention relates to a process for the preparation of POSs as defined above. This process is characterized in that it essentially consists in oxidizing the polysiloxane precursors of the targeted peroxide POSs. This oxidation is carried out using at least one oxidant preferably chosen from the group comprising:

H ₂ O ₂ , O ₂ , O ₃ and their mixtures, These precursors -POS are distinguished from the peroxidic POSs targeted in that they comprise one or more F'po functions, Fpo precursors and consisting of: O

Q Q V '

D by carboxyl residues: with X 'corresponding to the same definition as that given for X above;

O O

D and / or by acid anhydride residues - C— O-

D and / or by aldehyde residues; D and / or by residues comprising Sulfur, Phosphorus,

Silicon or Boron; These ester or anhydride functions of the precursors - POS can be terminal or included in a cycle -

As indicated above, the polysiloxane precursors with F'po functions can be obtained by cohydroiysis of chlorosilanes and non-functionalized alkoxysilanes and chlorosilanes or alkoxysilanes functionalized with substituents E and G. The step which follows the cohydroiysis can be a polycondensation and a polymerization of the hydrolysis products, in the presence of cyclic diorganosiloxanes or a redistribution step in the presence of polydiorganosiloxanes. These classic POS syntheses by cohydroiysis / polycondensation / polymerization or by cohydroiysis / redistribution are described in particular in "W. NELL chemistry and technology of silicones. Edition Académie Press. 1968." According to a preferred alternative, the starting materials used can be hydrogenated polyorganosiloxanes which can be functionalized by reacting them according to a hydrosilylation reaction (addition with olefinic precursors of the substituents E and G). See above for more details on this hydrosilylation. According to a preferred characteristic of the invention, the precursors - POS which are subjected to an oxidation to obtain POS peroxides targeted are selected from the POSs carrying functional substituents E;

* anhydrides

* and / or carboxyls - preferably benzoyl - * and / or aldehydes - preferably benzaldehydes -

* and / or sulfonyles,

* and / or phosphorylates

* and / or siloxyls * and / or boroxides.

Even more preferably, the -POS precursors selected are:

=> carriers of E anhydrides, the oxidation being carried out using H O ₂ in the presence of a catalyst of the strong base type, preferably potassium hydroxide,

=> and / or carriers of E carboxylic - preferably benzoyl, the oxidation being carried out using H ₂ O ₂ in the presence of a catalyst of strong acid type.

In accordance with the invention, it appeared particularly advantageous that the precursors - POS present before the oxidation step making it possible to transform the

F'po en Fpo, a molar purity> 90%, preferably> 95%.

In practice, this purification step is carried out by any known and appropriate method such as, for example, devolatilization or fractional precipitation in an organic solvent such as methanol. With regard more specifically to the oxidation step, we have seen that the oxidizing agents could be hydrogen peroxide, oxygen, ozone and their mixtures.

In the case where the oxidizing agent consists of hydrogen peroxide, the catalyst used can be a strong base, for example, an inorganic base such as

KOH or NaOH or else a strong acid, for example, a mineral acid such as H ₂ SO ₄ or an organic acid such as MeSO ₃ H. The solvents used in these cases are, for example, acetate ethyl or Me SO ₃ H.

As soon as the oxidizing agent is oxygen, it is possible to use a catalyst comprising Co ²⁺ .

In practice, this oxidation step can take place at ambient temperature and pressure.

The present invention also relates to POS precursors with F'po precursor function as defined above. These new POS precursors as such constitute intermediate products of the process according to the invention.

Finally, the present invention relates to the use of peroxide POSs as defined above by way of:

- bleaching agent,

- and / or disinfectant,

- and / or cleaning agent,

- And / or polymerization initiating agent, - and / or epoxidation agent.

The peroxide POSs according to the invention are particularly suitable as a bleaching agent and more particularly still as a bleaching agent for teeth, taking into account their properties of selectivity with respect to the teeth of non-toxicity, of controlled reactivity of the peroxide functions Fpo (limitation of the production of free radicals), of non-toxicity and of high efficiency at low dose.

From which it follows that the present invention also relates to a dental composition (for example an oral composition) - in particular toothpaste - characterized in that it comprises peroxygenated POSs as defined above by way of bleaching agent.

Without being limiting, we can give some details which define qualitatively and quantitatively the dental composition according to the invention by indicating that the latter contains: peroxygenated POS in an amount of 0.1 to 40% by weight, preferably of 0.1 to 10% by weight, and more preferably still on the order of 1 to 5% by weight; - polishing abrasives at a rate of 5 to 40% by weight, preferably from 5 to 35% by weight, these abrasives can be in particular silica, precipitated calcium carbonate, magnesium carbonate, calcium phosphates, oxides of zinc or tin titanium, talc, kaolin, abrasive particles comprising a core of calcium material, preferably calcium carbonate and a shell of an idrophobic product, preferably a fatty acid salt and more preferably still Na stearate; one or more fluorinated compounds corresponding to a concentration of the order of 0.005 to 2%, preferably from 0.1 to 1% by weight of fluorine in said composition, these fluorinated compounds possibly being in particular the salts of monofluorophosphoric acid in particular those of sodium potassium, lithium, calcium, aluminum, and ammonium or the fluorides of alkali metals, of sodium in particular; optionally anionic, nonionic, amphoteric or zwitterionic surfactants, at a rate of about 0.1 to 10%, preferably about 1 to 5% of the weight of said composition; we can cite, by way of example:

* anionic surfactants such as sodium, magnesium, ammonium, ethanolamine salts, Cg-Cis alkyl sulphates which may optionally contain up to 10 oxyethylene and or oxypropylene units (especially sodium lauryl sulphate) alkyl sulphoacetates C ₈ -Cιg (including sodium lauryl sulfoacetate) alkyl sulphoacetates C ₈ -Cι ₈ (particularly sodium dioctylsulfosuccinate) alkyl sarcosinates, C ₈ -Cι ₈ (sodium lauryl sarcosinate particular) alkyl phosphates, C ₈ ₈ may -Cι optionally contain up to 10 oxyethylene and or oxypropylene alkyl ether C ₈ -Cι ₈ carboxylate units containing up to 10 oxyethylene and or oxypropylene units sulfated monoglycerides * nonionic surfactants such as fatty sorbitan esters optionally polyethoxylated , ethoxylated fatty acids, polyethylene glycol esters, or polyether fatty alcohols, * amphoteric surfactants such as betaines, sulfobetaines optionally water at a rate of about 0.1 to 50%, preferably about 0 , 5 to 40% of the weight of said composition, optionally humectants, at a rate of approximately 10 to 85%, preferably from 10 to 70% of the weight of the said composition, humectants such as glycerol, sorbitol, polyethylene glycols, lactilol, xylitol optionally thickening agents such as certain silica used for this purpose (TIXOSIL 43 ^® marketed by RHONE-POULENC) at a rate of 5 to 15% by weight and / or polymers used alone or in combination as xanthan gum, guar gum, cellulose derivatives (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose), polyacrylates crosslinked such as CARBOPOL ^® distributed by Goodrich, alginates or carrageenans, VISCARIN ^® , at a rate of 0.1 to 5% by weight, optionally of bactericidal, anti-microbial, anti-plaque therapeutic agents, such as zinc citrate, polyphosphates, guanidines, bis-biguanides or other organic compound cationic therapy, possibly flavoring agents (essence of anise, star anise, mint, genius vre, cinnamon, cloves, rose,), sweeteners, colors (chlorophyll), preservatives omposition toothpaste subject of the invention, may occur > in different forms (pasta, gels, creams), prepared using conventional methods, and in various packaging (eg mono or dual compartment).

The peroxidized or peroxygenated POSs according to the invention are not only suitable for whitening and cleaning the teeth. In fact, they have been found to be quite effective as bleaching agents in detergent compositions. The present invention therefore also relates to detergent compositions comprising peroxygenated POSs or peroxides according to the invention as defined above, as bleaching agents.

The present will be better understood with the aid of the nonlimiting examples which follow and which also highlight certain of the advantages and the variant embodiments of the invention. These examples present the preparation of the POS precursors of the peroxide POSs according to the invention, the transformation by oxidation of these precursors into the peroxide POS, and the evaluation of the latter in terms of storage stability and whitening power.

EXAMPLES

Example 1: preparation of a precursor - POS (B) of a peroxide POS according to the invention, this precursor being a polydimethylsiloxane with trimethylsilyl ends and carrying functional substituents of the -propyl-oxy-benzoic type

starting silicone oil final silicone oil

• Si-O— Si-0-- Si- 0- + Si- Si-O— Si-O-HSi 0-4- Si—

H

structure A structure B

1.1 Synthesis of allyloxybenzoic acid

500 ml of distilled water, 51 of ethanol are charged into a 10-liter reactor equipped with a condenser, a dropping funnel, a mechanical stirrer, a thermometer probe and under an argon sky. absolute and gradually 450.9 g of potash (8.02 moles) with vigorous stirring (240 rpm) Once the potash is dissolved, 558.3 g of 4-hydroxy benzoic acid (4.04 moles) are loaded. The mass reaction cloudy then becomes clear The allyl bromide (489.0 g or 4.04 moles) is then poured in 2 h at room temperature After pouring, the reaction medium is brought to 80 ° C for 17 hours

After returning to ambient temperature, the reaction medium is neutralized by gradual addition over 1 hour 30 minutes of 1 liter of 36% hydrochloric acid (11 moles). The reaction medium becomes milky and it is filtered on frit No. 4 under vacuum. A white filter cake is obtained which is washed with water (250 ml). In order to purify the allyloxybenzoic acid present in the filter cake, the process is carried out by recrystallization. In the 10 l reactor, the cake is loaded. filtration, 5 1 of absolute ethanol and 750 ml of distilled water. The reaction mass is brought to reflux (80 ° C.) and distilled water is gradually added until a single clear phase is obtained, ie 1.75 1 of distilled water. The reaction mass is then transferred to a 10 l container. which is cooled by ice The medium is left to recrystallize for 16 h then filtered on a No. 4 frit under vacuum The cake is washed with distilled water (2 I used in three times) Crystals are obtained which are dried under vacuum of 200 mmHg and at 70 ° C. The yield is 35%

1 2 Protection of allyloxybenzoic acid by a trimethylsilyl group In a three-necked flask of 250 ml provided with a condenser, a mechanical stirring, a thermometer probe and under an argon sky, 53.62 g of allyloxybenzoic acid prepared in 1 1 (0.3 mole) and 120.58 g of hexamethyldisilazane (0.75 mole) are poured in over 1 hour The reaction medium is left in contact at 130 ° C. for 24 hours. After return to room temperature a solution of protected allyloxybenzoic acid in solution in hexamethyldisilazane Protected product can be purified by vacuum distillation

1.3. Hydrosilylation of protected allyloxybenzoic acid

87.01 g of the protected acid solution are introduced into a 250 ml three-necked flask fitted with a condenser, a dropping funnel, a mechanical stirrer, a thermometer probe and under an argon sky. obtained in 1.2 (0.15 mole of protected acid) and 31.0 mg of platinum catalyst The reaction medium is brought to 80 ° C. and stirred. Then, the reaction medium is poured in 45 minutes 35.03 g d oil of structure A (0.13 mole of SiH function) The reaction medium is then left in contact for 16 hours During this contact time, 7.5 mg of PtCl ₂ (PhCN) _{2 are added} .

At 85 ° C., 2% by mass of carbon black is added which is left in contact for 16 hours. After returning to ambient temperature, the reaction medium is filtered on a cardboard filter under pressure and then the reaction mass is returned to a single-color flask provided with a magnetic bar. The product is isolated by devolatilization at 120 ° C. under a vacuum of 1 mmHg

The product thus isolated is deprotected by hydrolysis with distilled water (200 ml) which is poured onto the product to be deprotected in lhl5 and heating at 90 ° C. 16 hours The medium becomes whitish The water is removed at 1 10 ° C under vacuum of 2 mmHg for 4 h 5 5 We then obtain 58.40 g of hydrosilylated oil of structure B

1 4 Purification of a silicone oil B with benzoic acid functions

We start from a pure oil at 92% by mass with 8% by mass consisting of ungrafted oligomers originating from ungrafted allyloxybenzoic acid or isomers of allyloxybenzoic acid. Among the various purification techniques, several are possible. implemented here is the fractional precipitation It is a question of dissolving the grafted oil obtained in 1 3 in a hot alcohol This alcohol can be more particularly methanol Then the polymer is precipitated by adding water of basic pH L ' operation is repeated another time The third operation consists in hot dissolving the silicone polymer in methanol and then adding water at acidic pH. The polymer thus purified is heated to 115 ° C. under a vacuum of 20 mmHg in order to remove the water or residual alcohol The product is finally placed in an oven at 100 ° C under atmospheric pressure. A polymer of purity greater than 95% by weight is obtained.

Example 2: Preparation of a precursor - POS (C) of a peroxide POS according to the invention, this precursor being a polydimethylsiloxane with trimethylsilyl ends and carrying functional substituents of the -propyl- succinic anhydride type

starting silicone oil final silicone oil

structure A

Synthesis of silicone oil C with succinic anhydride units:

119.53 g of pure succinic allylanhydride are introduced into a 500 ml three-necked flask fitted with mechanical stirring, a condenser, a dropping funnel, a temperature probe and under argon sweeping. more than 99 mol% (0.85 mol) and 44.2 mg of Karstedt platinum at 10% by mass of platinum. The reaction medium is brought to 90 ° C. with stirring, then 175.53 g of oil of structure A (0.66 mole of SiH function) are poured in 1 h 25. The reaction medium is left in contact at 90 ° C. with stirring for 4 hours. The reaction medium is then treated with 2% by weight of carbon black at 70 ° C for 4 hours. After returning to ambient temperature, the reaction medium is filtered on cardboard under nitrogen pressure. After placing the reaction medium in a single-necked flask fitted with a magnetic bar, the grafted silicone polymer is isolated by devolatilizing the excess oligomer by heating to 180 ° C. under a vacuum of 2 mmHg. A silicone oil of structure C and of purity equal to 94% by weight is obtained. To purify this product to more than 99% by weight of purity, the product was devolatilized using a 10 ^"3 mmHg vacuum diffusion pump by heating the polymer from 120 to 160 ° C for 6 hours A succinic propylanhydride grafted silicone polymer is then obtained with a purity greater than 99% by weight, the infrared analysis shows that the anhydride is not open during the treatments described in the examples.

Example 3 Preparation of a POS Precursor (E) of a Peroxide POS According to the Invention, This Precursor Being a Polydimethylsiloxane with Trimethylsilyl Ends and Carrying Functional Substituents of the -propyl-succinimide-benzoic Type

starting silicone oil final silicone oil

3 1 Preparation of amino function silicone by coequilibration

50 g of aminopropyldimethoxymethylsilane (0.3 mole) are introduced into a three-necked flask equipped with a devolatilization system, a mechanical stirrer, a dropping funnel, a temperature probe and under an argon sky and a quantity of 27.6 g of water (1.5 mole) is added over 1 hour. The mixture is brought to 1 10 ° C. and devolatilized under 11.1 mmHg in order to collect the quantity of methanol of 19.2 g.

After returning to temperature and having replaced the distillation system with a refrigerant, in addition to 35.1 g of hydrolyzed silane previously obtained, 30.5 g of octamethyltetrasiloxane (0.1 mol or 10% excess) are introduced. , 34.3 g of a short silicone oil with 6 silicones of formula MD ₄ and 5.3 g of potassium siliconate at 15% by weight of potassium hydroxide (80 ppm) After heating at 130 ° C for 6 hours under nitrogen stripping, the reaction mixture is neutralized by adding 12.3 g of a solution of silicon ester of phosphoric acid at 9% by mass of phosphoric acid. Following neutralization, the medium is left in contact for 30 minutes at 80 ° C. and then devolatilized under 2 mmHg at 170 ° C. 113.5 g of silicone oil of structure D are obtained.

3.2. Formation of a silicone E with acid and imide functions

28.8 g of is charged into a three-necked flask provided with a condenser, a mechanical stirrer, a dropping funnel, a thermometer probe, a Dien Stark system. trimellic anhydride (0.15 mol), and 75 g of toluene and 50.0 g of silicone oil with an amino function of structure D (0.15 mol of amino function) are poured in over 1 hour. The reaction mixture is left in contact at room temperature for 1 hour and then the reaction mixture is brought to reflux for 5 hours over time, the elimination of water is followed. After returning to ambient temperature, the reaction mixture is filtered on cardboard and under pressure. After placing the latter in a single-color flask fitted with a magnetic bar, the solvent is devolatilized by heating to 110 ° C. under a vacuum of 10 mmHg. A polymer of structure E pure at 95% by weight is obtained.

EXAMPLE 4 PREPARATION OF A PRECURSOR - POS (F) OF A POS PEROXIDE ACCORDING TO THE INVENTION, THIS PRECURSOR BEING A POLYDIMETHYLSILOXANE WITH TRIMETHYLSILYL EXTREMITIES AND CARRIER OF AMINOETHYLAMIN _2- TYPE 2- ( ₂ ) AMINOETHYLAMINOPHYLAMIN NH- (CH ₂ ) 3-).

Example 3 is reproduced with the difference that the aminopropyldimethoxymethylsilane used in point 3.1 is replaced. for aminoethylaminopropyldimethoxymethylsilane and a precursor - POS or silicone oil F is obtained in fine: EXAMPLE 5: OBTAINING A PEROXIDE POS IN WHICH THE FPO FUNCTIONS

(-O-O-) SUBSTITUENTS E ARE INCLUDED IN PERACID REMAINS

O

CARBOXYLICS ( ^{_ C} ° ° ^H 'FROM THE POS PRECURSOR ACCORDING TO EXAMPLE 2 (REMAINING ANHYDRIDE REMAINS) 5.1 Test

In a weighing tube weigh 250 mg of silicone oil C from Example 2, i.e. 0.615 mmol of anhydride functions (4 functions per polymer) add 0.5 ml of ethyl acetate (AcOEt), weigh 45 mg d hydrogen peroxide at 70% or 0.926 mmol (excess 1.5 equivalent relative to the stochiometry which is 1 H 0 per anhydride). introduce 1 drop of KOH (IN). add a small magnetic bar. shake at room temperature for 1 hour

5.2. Treatment add 3 ml AcOET transfer to a small 50 ml separating funnel add 3 ml of permuted water to 100 g / 1 of ammonium sulphate shake, allow to settle, eliminate the lower aqueous phase repeat the operation again 2 times recover the organic phase in a 50 ml beaker, add 1 g of anhydrous MgSO transfer to a tared flask of 50 ml, rinse the ampoule twice and MgSO4 with 1 ml of ACOE and dry draw with Rotavapor, bath at 35 ° max draw a few minutes under vacuum pump, cold (room temperature) weigh the product obtained

5 3 Determination of peroxides in peroxidized silicone oil

METROHM Dosimat 665 device

5.3 1. Procedure In 50 ml Erlenmeyer weigh about 250 mg of peroxidized oil add - 20 ml of ACETIC ACID / H ₂ O 80/20 mixture and dissolve - or better 20 ml of pure acetic acid, dissolve, then add a little water add 1 spatula (1g) of NaHCO (inerting with CO ₂ ) add 1 spatula (lg) of potassium iodide butcher and put in the dark for 20 minutes minimum

Transfer to a 150 ml beaker (tall form) rinse with 50 ml of distilled water add acetone (maintains solubility and defoaming) add a magnetic bar and put in place, determination of the iodine released by a solution SODIUM THIOSULFATE 0, 1 N

5 3 2 Calculations

No. mmoles H ₂ O ₂ = Vml x CO3 x CO2 / COO x COI% weight H ₂ O = No. mmoles dosed x 34/1000 1 H ₂ O ₂ equivalent ≈ 1 R-CO-O-OH equivalent

5 3 3 Expression of the results% by weight in H ₂ O ₂ equivalent Since the precursor -POS (oil - C -) prepared in Example 2 comprises the substituents E each carrying an anhydride, and which is assumed the reaction is complete (oxidation yield = 100%), then for one mole of oil (- C -), 4 moles of H ₂ O ₂ are reacted, ie in% by weight 1 mole oil (- C -) = 1628 g, for 4 moles H ₂ O ₂ = 136 g, or 8.35% by weight of H ₂ O ₂

5 3 4 Result The peracid content of the oxidized oil C is 6.2%, i.e. an oxidation of

6.2 / 8.35 x 100 = 74%

EXAMPLE 6: OBTAINING A PEROXIDE POS IN WHICH THE FPO FUNCTIONS

(-O-O-) SUBSTITUENTS E ARE INCLUDED IN PERACID REMAINS

O

CARBOXYLIC ( ^{~~ C} ° 'FROM THE PRECURSOR POS ACCORDING TO

EXAMPLE 2 (REMAINING ANHYDRIDE REMAINS)

In a 100 ml flask, load 15 g of oil C from Example 2 (36.9 mmol anhydride) 30 g of ethyl acetate 2.7 g of hydrogen peroxide 0 70% (55.6 mmol ( x 1.5)) 0.6 ml KOH N (0.6 mmol) Put a magnetic bar and shake. The exotherm is immediate, the temperature reaches 31 ° C.

Place a crystallizer of cold water to bring it to room temperature Maintain for 1 hour

Transfer to 100 ml separating funnel, rinse the flask twice with 10 ml of AcOEt

Proceed to 8 washes with 20 ml of water permuted to 100 g / 1 of ammonium sulphate: the disappearance of hydrogen peroxide in the aqueous phases is followed by indicator paper for peroxides. Dry over anhydrous MgSO Filter through sintered glass

Transfer to a 100 ml flask, rinse the vial and the frit. Draw to dry with rotovapor, bath at 35 ° axi

Dry under vacuum pump for 3 hours at room temperature. Weight obtained: 15.4 g

Peracid content: 5.46% (expressed as H ₂ O ₂ ) Oxidation: 65%

EXAMPLE 7 STUDY OF THE STABILITY OF STORAGE OF POS PEROXIDES IN ACCORDANCE WITH THE INVENTION

The POS used is prepared according to the methodology given in Example 6 The product is stored dried at 5 ° C and 25 ° C

Samples are taken over time and in dose the peroxides as described above in 5.3 7 1 Storage at 5 ° C from 0 to 30 days

The results are given in Table 1 below

Table 1

7.2. Storage at 5 ° C, 0, 1 1 and 22 days

The results are given in Table 2 below

Table 2

EXAMPLE 8: OBTAINING A PEROXIDE POS IN WHICH THE FPO FUNCTIONS

(-O-O-) SUBSTITUENTS E ARE INCLUDED IN PERACID REMAINS

O

II

CARBOXYLICS * ° ^ ^{w π;} FROM THE POS PRECURSOR AS IN EXAMPLE 2 (REMAINING ANHYDRIDES REMAINING)

Example 5 is reproduced with the difference that no KOH is used. Results:

H ₂ O ₂ equivalent content = 0.59% oxidation ^• 7%

EXAMPLE 9: OBTAINING A PEROXIDE POS IN WHICH THE FPO FUNCTIONS

(-O-O-) SUBSTITUENTS E ARE INCLUDED IN PERACID REMAINS

O

II

CARBOXYLICS (-c- -O — O— H) ^" 'FROM THE PRECURSOR POS AS EXAMPLE 2 (REMAINING ANHYDRIDES REMAINING)

Example 6 is reproduced with the difference that the drop of KOH is replaced by a drop of H ₃ PO ₄ (85% in water). Results ''

H ₂ O ₂ equivalent content = 1.03% oxidation. 12% EXAMPLE 10: OBTAINING A PEROXIDE POS IN WHICH THE FUNCTIONS

OPS (-o-o-) SUBSTITUTES E ARE INCLUDED IN PERACID REMAINS

O

CARBOXYLICS ( ^{"~ C} ° ° ^H FROM THE POS PRECURSOR ACCORDING TO EXAMPLE 1 (PENDANT BENZOIC RESIDUES) 10 1 Test

In a weighing tube weigh 250 mg of silicone oil B from Example 1, ie 0.578 mmol of acid functions (4 functions per polymer) add 0.5 ml of ethyl acetate (AcOEt),. weigh 84 mg of hydrogen peroxide at 70% or 1.729 mmol (excess 3 equivalents compared to the stochiometry which is 1 H ₂ 0 ₂ per acid). 1 drop H ₂ SO ₄ (95% in water). add a small magnetic bar

. shake at room temperature for 2 hours, in the presence of an excess anhydrous MgSO4 (> 100 mg).

10 2 Treatment add 3 ml AcOET transfer to a small 50 ml separating funnel add 3 ml of permuted water to 100 g / 1 of ammonium sulphate shake, leave to settle, eliminate the lower aqueous phase repeat the operation again 2 times recover the organic phase in a 50 ml beaker, add 1 g of anhydrous MgSO ₄ transfer to a 50 ml tared flask, rinse the ampoule 2 times and MgSO4 with

1 ml of ACOE and draw dry with Rotavapor, bath at 35 ° axi draw for a few minutes under vacuum pump, cold (room temperature) weigh the product obtained

10 3 Result

Peracid content 0.66% oxidation 9% EXAMPLE 11: EVALUATION OF THE WHITENING POWER OF THE POS PEROXIDE OF EXAMPLE 6

11.1 Developing method for determining the whitening power on PAH hydroxyapatite powder

11.1.1. Principle

* Measurement of the whitening power of oxidizing compounds, on a hydroxyapatite PAH powder, previously fouled with a hot tea solution.

* Whitening power quantified by colorimetric measurements performed on the Minolta CR-241 device.

11.1.2. Apparatus A - Small utensils

* Filter paper, "rapid filtration" n ° 41 from Whatman for the filtration of the tea solution and for the recovery of dirty powder

* Filter paper. GF / C 47 mm diameter from Whatman used for recovery of bleached powder * Bϋchner (diameter of 100 or 160 mm), 2 L vacuum flask, vacuum pump or water pump with differential pressure gauge, rubber seals

* Crystal polystyrene jars (transparent), capacity of ~ 40 ml

B - Devices * Minolta CR-241 colorimeter

* Promax 2020 back-and-forth agitator * Oven (50 to l00 ° C)

C - Products * Deionized water

* Lipton Yellow tea, quality n ° l

* HAP BIO-RAD hydroxyapatite powder

* Solution or oxidant 11.1.3. Procedure

A - Contamination of the PAH powder a - Measurement of the initial whiteness of the powder A measurement of the initial whiteness of the PAH powder is carried out. It is performed on the Minolta CR-241 device. Three measurements are made to obtain an average value of Lo, ao, bo.

b - Tea decoction, filtration

In a 1000 ml beaker, 500 ml of deionized water and 10 cut tea bags are introduced (C = ~ 40g / l) and brought to ~ 80 ° C with mechanical stirring (200 rpm) for 90 minutes.

Stirring and heating power are stopped. Once the medium has cooled to ~ 40 ° C

(time required = ~ 90 min), it is vacuum filtered.

The filtrate (= fouling tea solution) is collected. Its volume is readjusted to 500 ml with deionized water.

c - Fouling

7.5 g of PAH powder are introduced into the tea solution.

The whole is again brought to ~ 80 ° C, with stirring for 45 minutes. Heating and stirring are stopped, the medium cools with ambient air (up to ~

40 ° C) before being vacuum filtered.

The powder is washed with three times 20 ml of hot deionized water until the filtrate is colorless.

The filter and the powder are placed in an oven [T = 50-100 ° C] until the water has completely evaporated.

The powder recovered in the form of agglomerates is ground using a mortar and pestle.

Its new whiteness is measured (Ls, as, bs) with the Minolta CR-241.

B - Whitening of dirty PAH powder

6.5 g of oxidizing solution (containing the equivalent of 0.3% of H ₂ O ₂ ) and 50 mg of dirty PAH powder are transferred to a crystal polystyrene bottle with a capacity of ~ 40 ml.

The whole is placed on the PROMAX 2020 back-and-forth agitator for the desired time (15 min, 30 min, 1h, 2h, ...) at the rate of 250 round trips.

The medium is then diluted by adding 20 ml of ethanol before being filtered.

The powder is washed with three times 30 ml of ethanol. The whole filter + bleached powder is dried in the open air in a hood.

The new whiteness of the bleached powder can be measured (Le), and the whitening power of the oxidizing solution can be calculated.

1 1.1.4 Calculations

The bleaching power of the oxidizing compound is calculated from the value

L given by the colorimeter, and obtained after the various treatments of the powder

PAH.

L * represents the clarity of the sample, its values range between 0 and 100.

We thus define the different values:

* Lo, initial clarity before fouling.

* Ls, clarity after fouling.

* The clarity after whitening.

The whitening power is calculated as follows: π Whitening power:

The - Ls

Pb -x lOO

Lo - Ls

11.2 Measurement of the whiteness The obtained in the test described in 11.1 above, with the peroxide POS of Example 6

11.2.1. The bleaching of the PAH powder according to point 1 1.1.3 B above is carried out as follows:

6.5 g of oxidizing preparation containing 300 mg of POS peroxide according to Example 6 dispersed in 6.2 g of reverse water by manual stirring. and 50 mg of contaminated PAH powder are transferred to a 40 mg crystal polystyrene bottle.

Then proceed as indicated in point 11.1.3. B. 11.2.2 Results Table 3

_ „, Lc- Ls

* Pb = 100

Lo - Ls Ls = 50 and Lo = 92

Claims

CLAIMS:

1 - Polyorganosiloxanes (POS) comprising siloxane units of formula:

R ^{g G} c ^Si0 4 - (a + _{b +} c>

(I) ² - ”in which:

D a + b + c = 0 to 3

D a, b, c = 0 to 3

DR corresponds to one or more identical or different radicals, R being chosen from monovalent hydrocarbon groups, preferably from linear, branched and / or cyclic alkyls and / or aryls, and more preferably still from linear or branched C1 alkyls -C4 and phenyl, xylyl and tolyl groups;

DE corresponds to one or more functional substituents which are identical or different from one another, monovalent, carrying one or more peroxo (-OO-) Fpo functions, and optionally each comprising one or more Fstab stabilizing Fpo functions, which are identical or different from one another and chosen from among the functions capable of binding via weak links with the Fpo functions;

DG corresponds to one or more identical or different functional substituents with each other and each comprising one or more Fstab stabilizing functions of Fpo, identical or different between them and chosen from the functions capable of binding via weak bonds with the Fpo functions ;

- with the conditions according to which:. (i). the concentration of functions [Fpo] expressed by the ratio number Fpo total number of silicon atoms in the POS is defined as follows:

Δ 0 <[Fpo]

Δ preferably 0.01 <[Fpo] <1.0 Δ and more preferably still 0.1 <[Fpo] <0.6.

. (ii). the concentration in molar% of siloxane units T (a + b + c = 1) and / or Q (a + b + c = 0) is defined as follows:

Δ 0 <[T and / or Q] <20

Δ preferably 0 <[T and / or Q] <10 Δ and more preferably still, 0 <[T and / or Q] <8. 2 - Polyorganosiloxanes according to claim 1, characterized B in that the substituents E of the units (I) are identical or different between them are chosen from groups (cyclo) aliphatic and / or aromatic and / or heterocyclic hydrocarbons optionally comprising one or more heteroatoms - preferably O, N, S Si-, these groups possibly being substituted;

B and in that Fpo is included: either in an acyl peroxide

- C— OOX

II O

- C— OOX is in an acyl peroxide. ^ with X corresponding to H, representing a monovalent hydrocarbon radical, that is to say comprising, inter alia, hydrogen and carbon atoms, aliphatic and / or alicyclic and / or aromatic and / or heterocyclic optionally comprising one or more heteroatoms (N, O, S ...), this radical possibly being substituted;

R ^x may possibly correspond to the same definition as that given above for R in formula (I), to a halogen preferably chlorine or to a cation making it possible to form a salt with the peroxo anion and preferably chosen from the elements of columns la and IIA of the periodic table,

> either in a peroxide residue comprising sulfur, silicon phosphorus or boron as an oxygen carrier

3 - Polyorganosiloxanes according to claim 1 or claim 2, characterized in that, in the substituent (s) G of formula (I), the Fstabs correspond to functions which can generate weak bonds (hydrogen bonds) with Fpo, and selected in the group comprising:

- the functional units comprising nitrogen and / or oxygen and / or fluorine, and / or sulfur and / or phosphorus; the carboxylic, carboxylate, amide, imide, sulfonamide, hydroxyl, alkoxyl, amino or organofluoric units being preferred,

- »cationic units, preferably those comprising one or more quaternary ammoniums; - chelating units comprising one or more ether functions and / or one or more amino functions, and / or phosphonate and / or sulfonate chelating units 4 - Polyorganosiloxanes according to any one of Claims 1 to 3, characterized in that they correspond to the formula (ϋ) given below:

(II) R ¹ ₃ SiO [SiR ^ OJ ^ .SiR ^ O] - [SiR ² GC ^ -SiR, ³ 3

in which :

. R ¹ , R ³ independently representing a hydrogen, a hydroxyl or a monovalent residue corresponding to the same definition as that given for R above;

. R independently represent hydrogen, a hydroxyl or a monovalent residue corresponding to the same definition as that given for R above;

2 <m + n + o <300 preferably 3 <m + n + o <50 and more preferentially still 5 <m + n + o <20

0 <m <200 preferably 1 <m <100 and more preferably still 1 <m <10

0 <n <50 preferably 1 <n <10 and more preferably still 2 <n <4

0 <o <50 preferably 1 <o <10 and more preferably still 2 <o <4.

5 - Polyorganosiloxanes according to claim 4, characterized in that:

Δ R ¹ , R ³ = CC ₃ alkyl, preferably - CH ₃ Δ R ² = CC ₃ alkyl, preferably - CH ₃ Δ the functional substituent (s) E, comprise both Fpo and Fstab functions.

6 - Polyorganosiloxanes according to any one of claims 1 to 5, characterized in that E comprises, in addition to the Fpo (s), at least one bicarboxylated and / or benzoxyl and / or imide unit. 7 - Process for the preparation of POS according to any one of claims 1 to 6, characterized in that it consists essentially in oxidizing precursors polysiloxane of POS according to any one of claims 1 to 6, using at least one oxidant preferably chosen from the group comprising:

H ₂ O ₂ , O ₂ , O ₃ and their mixtures, these -POS precursors which differ from the targeted peroxide POSs in that they comprise one or more F'po functions Fpo precursors and consisting of:

Q Q V '

D by carboxyl residues: with X 'corresponding to the same definition as that given for X in claim 2:

O O

D and / or by acid anhydride residues: - c— O-

D and / or by aldehyde residues;

D and / or by oxide residues comprising Sulfur, Phosphorus, Silicon or Boron;

8 - Process according to claim 7, characterized in that the precursors - POS which are subjected to an oxidation to obtain POS peroxides targeted are selected from the POS carrying functional substituents E:

* anhydrides

* and / or carboxyls - preferably benzoyl -

* and / or aldehydes - preferably benzaldehydes - * and / or sulfonyles,

* and / or phosphorylates,

* and / or siloxyls

* and / or boroxides.

9 - Method according to claim 8, characterized in that the -POS precursors selected are:

=> carriers of E anhydrides, the oxidation being carried out using H ₂ O ₂ in the presence of a catalyst of the strong base type, preferably potassium hydroxide;

=> and / or carriers of carboxylic E - preferably benzoyl-, the oxidation being carried out using H ₂ O ₂ in the presence of a catalyst of strong acid type. 10 - Process according to any one of claims 1 to 9, characterized in that one implements precursors - POS of molar purity> 90%, preferably> 95%.

11 - POS precursors as defined in any one of claims 7 to 10.

12 - Use of POS peroxides according to any one of claims 1 to 6 and / or obtained by the process according to any one of claims 7 to 10 as:

- bleaching agent, - and / or disinfecting agent,

- and / or cleaning agent,

- and / or polymerization initiating agent,

- And / or epoxidation agent.

13 - Dental composition - in particular toothpaste - characterized in that it comprises peroxygenated POS according to any one of claims 1 to 6 and / or by the method according to any one of claims 7 to 10, by way of bleaching agent.

14 - washing compositionUe characterized in that it comprises peroxygenated POS according to any one of claims 1 to 6 and / or by the method according to any one of claims 7 to 10, as a bleaching agent.