EP3237070A1

EP3237070A1 - Organopolysiloxanes and methods for preparing same

Info

Publication number: EP3237070A1
Application number: EP15820515.3A
Authority: EP
Inventors: François GANACHAUD; Etienne Fleury; Daniel PORTINHA DE ALMEIDA; Aymeric GENEST; Emmanuel POUGET
Original assignee: Centre National de la Recherche Scientifique CNRS; Universite Claude Bernard Lyon 1 UCBL; Bluestar Silicones France SAS; Institut National des Sciences Appliquees de Lyon; Universite Jean Monnet Saint Etienne
Current assignee: Centre National de la Recherche Scientifique CNRS; Universite Claude Bernard Lyon 1 UCBL; Institut National des Sciences Appliquees de Lyon; Universite Jean Monnet Saint Etienne; Elkem Silicones France SAS
Priority date: 2014-12-22
Filing date: 2015-12-21
Publication date: 2017-11-01
Also published as: FR3030536A1; JP6673934B2; CN107429063B; KR20190093710A; WO2016102498A1; US10358541B2; FR3030536B1; KR102098731B1; US20180265668A1; KR20170134315A; CN107429063A; JP2020023703A; JP2018501393A

Abstract

The present invention concerns an organopolysiloxane (A) able to be obtained by the reaction, at a temperature of between 10°C and 75°C, between - at least one compound (C) chosen from the organic compounds comprising at least one alkene or alkyne functional group, at least one of the substituents of which is an acid functional group and the organic compounds comprising at least one acid functional group and at least one alkene or alkyne functional group, at least one of the substituents of which is an electron-withdrawing group; and - at least one organopolysiloxane (B) chosen from the organopolysiloxanes comprising siloxyl units (I.1) and (I.2) of the following formulae: (I) The present invention also concerns compositions comprising said organopolysiloxanes (A) and the uses thereof.

Description

Organopolysiloxanes and process for their preparation

The present invention relates to an organopolysiloxane (A), its process of preparation, the compositions comprising it and its use in particular as adhesion promoter, anti-mist additive, antifoam additive, electrical conductor, antistatic additive, antibacterial additive, anti- corrosion, fireproof or for thin film coating. Many approaches have been developed to provide modified organopolysiloxane compounds. The main objective is to provide organopolysiloxane compounds with varied viscoelastic properties in order to adapt to various uses, especially as an elastomer, in a paper or film coating composition, as an adhesion promoter, as an anti-fog additive etc.

There is therefore an interest in providing organopolysiloxane compounds having modulable viscoelastic properties in order to adapt to any type of use.

There is also an interest in providing a simple and economical method for the preparation of organopolysiloxane compounds having modulable viscoelastic properties.

These objectives are fulfilled by the present application which relates to an organopolysiloxane (A) obtainable by reaction, at a temperature of between 10 ° C. and 75 ° C., between:

at least one compound (C) chosen from organic compounds comprising at least one alkene or alkyne function of which at least one of the substituents is an acid function and organic compounds comprising at least one acid function and at least one alkene function or alkyne of which at least one of the substituents is an electron-withdrawing group; and

at least one organopolysiloxane (B) chosen from organopolysiloxanes comprising siloxyl units (1.1) and (I.2) of the following formulas:

There _is ¾si¾ ^ z _c ² sio ^

² (M); ² (i.2) in which :

- a = 1 or 2, b = 0, 1 or 2 and a + b = 1, 2 or 3

- c = 1, 2, 3 or 4

the symbols Y, identical or different, represent a functional group of formula (I.3):

-E- (NH-G) _h - (NH ₂ ) i (I.3)

in which :

- h = 0 or 1;

i = 0 or 1;

- h + i = 1 or 2

E represents a divalent aliphatic, cycloaliphatic or aromatic hydrocarbon radical comprising from 1 to 30 carbon atoms; preferably aliphatic containing from 1 to 10 carbon atoms;

when present, G represents an aliphatic hydrocarbon radical comprising from 1 to 10 carbon atoms, monovalent when i = 0 or divalent when i = 1;

the symbols Z ¹ and Z ² , which are identical or different, represent a monovalent hydrocarbon radical having from 1 to 30 carbon atoms and optionally comprising one or more unsaturations and / or one or more fluorine atoms, a hydroxyl group, or a radical; -OR ¹ with R ¹ which represents a linear, cyclic or branched C1-C10 hydrocarbon radical, and preferably Z ¹ and Z ² represent a monovalent hydrocarbon group chosen from the group consisting of alkyl groups having from 1 to 8 carbon atoms; carbon, alkenyl groups having 2 to 6 carbon atoms and aryl groups having 6 to 12 carbon atoms optionally comprising one or more fluorine atoms, a hydroxyl group, or a radical-OR ¹ with R ¹ which represents a linear, cyclic or branched C1-C10 hydrocarbon radical, and even more preferentially chosen from the group consisting of a methyl, ethyl, propyl, 3,3,3-trifluoropropyl, vinyl, hydroxyl, ethoxyl, methoxyl, xylyl, tolyl and phenyl;

said polyorganosiloxane (B) comprising, per molecule, at least one siloxyl unit (1.1) bearing at least one functional group of formula (I.3).

According to a particular embodiment, the organopolysiloxane (A) as described above is obtained at a reaction temperature of between 10 and 70 ° C., preferably between 15 and 70 ° C. In the context of the present invention, the term "electron-withdrawing group" is intended to mean a group which attracts electrons to itself, that is to say an atom or group of atoms having an electronegativity greater than that of hydrogen, thus resulting in to electron-depleted bonds. Thus, in the context of the invention, the electron-withdrawing group depletes the alkene or alkyne functions in electrons. A definition of such groups is in particular given in the publication "Michael adds reactions in macromolecular design for emerging technologies" Progress in Polymer Science 31 (5), 487-531 (2006). Among the electron-withdrawing groups, mention may be made especially of the ketone, acid, amide, phosphonate ester, phosphonic acid, sulphonic acid, sulphone, ester, thioester, NO ₂ group, CN group, etc. groups.

In the context of the present application, the term "acid function" is understood to mean in particular the carboxylic acid, sulphonic acid and phosphonic acid functions. Thus, and preferably, the compound (C) of the present invention is chosen from organic compounds comprising at least one carbon-carbon double or triple bond of which at least one of the substituents is a carboxylic acid, sulphonic acid or acid function. phosphonic acid or organic compounds comprising at least one acid functional group chosen from a carboxylic acid function, a sulphonic acid function or a phosphonic acid function and at least one carbon or carbon double or triple bond of which at least one of the substituents is a group electron. This compound C can then react according to an Aza-Michael reaction with primary or secondary amines as described in the publication "Michael addition reactions in macromolecular design for emerging technologies" Progress in Polymer Science 31 (5), 487-531 ( 2006). Preferably, the compound (C) according to the invention comprises at least one carbon-carbon double bond of which at least one of the substituents is a carboxylic acid function or comprises at least one carboxylic acid function and at least one carbon-carbon double bond. carbon of which at least one of the substituents is an electron-withdrawing group. Even more preferably, in the compound (C) according to the invention at least one of the carbon-carbon double bonds and at least one of the acid functions are conjugated.

Among these compounds, mention may be made preferably of the compounds of formula (II):

COOR ⁵ in which :

R ² , R ³ and R ⁴ , which may be identical or different, represent a hydrogen atom, a COOH group or a C 1 to C ₆ , preferably C 1 to C ₃ , alkyl group, preferably methyl; R ⁵ represents a hydrogen atom, an alkyl group or an aryl group, wherein the alkyl and aryl comprise at least one COOH group.

Preferably, in the compounds of formula (II),

R ² and R ³ , which may be identical or different, represent a hydrogen atom or a C ₁ to C ₆ , preferably C ₁ to C ₃ , alkyl group, preferably methyl;

R ⁴ represents a hydrogen atom, a C ₁ to C ₆ , preferably C ₁ to C ₃ , alkyl group, preferably methyl, or a COOH group;

R ⁵ represents a hydrogen atom, an alkyl group or an aryl group, wherein the alkyl and aryl comprise at least one COOH group.

Preferably, the compounds (C) of the invention are chosen from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, 2-carboxyethylacrylate, 3-carboxypropylacrylate, maleic acid, fumaric acid, 2- (acryloyloxy) acetic acid, 2- (acryloyloxy) propanoic acid, 3- (acrylolyloxy) propanoic acid, 2- (acryloyloxy) -2-phenylacetic acid, 4- (acryloyloxy) butanoic acid, 2- (acryloyloxy) -2-methylpropanoic acid, 5- (acryloyloxy) pentanoic acid, (E) -but-2-enoic acid, (Z) acid -propene-1-ene-1,2,3-tricarboxylic acid, cinnamic acid, sorbic acid, 2-hexenoic acid, 2-pentenoic acid, 2,4-pentadienoic acid, ethenesulfonic acid, vinylphosphonic acid, (1-phenylvinyl) phosphonic acid, 3- (vinylsulfonyl) propanoic acid, 2- (vinylsulfonyl) acetic acid, 2- (vinylsulfonyl) succinic acid, acetylene dicarboxylic acid and propiolic acid.

Preferably, the compounds (C) of the invention are chosen from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, 2-carboxyethylacrylate, 3-carboxypropylacrylate, maleic acid and fumaric acid.

Preferably, the compound (C) is acrylic acid or 2-carboxyethylacrylate.

Preferably, the compound (C) is acrylic acid.

Preferably, the organopolysiloxanes (B) may have a linear, branched, or cyclic structure. In the case of linear organopolysiloxanes, these consist essentially of "D" siloxyl units, chosen in particular from the group consisting of siloxyl units Y ₂ SiO _2/2 , YZ ¹ SiO _2/2 and Z ² ₂ Si0 _2/2 and siloxyl units "M", in particular selected from the group consisting of siloxyl units Y SiO _{_3/2,} SiO ₂ YZ ^_1/2, Y ₂ Z ¹ SiO _{/ 2} and Z ² SiO _{_3/2} , the Y, Z ¹ and Z ² being as defined above, being understood that the polyorganosiloxane (B) comprises, per molecule, at least one siloxyl unit bearing at least one functional group of formula (1.3) defined above.

In a particularly preferred embodiment, the organopolysiloxanes (B) are chosen from organopolysiloxanes comprising siloxyl units (1.1) and (I.2) of the following formulas:

There _is ¾si¾ ^ z _c ² sio ^

² (M); ² (i.2)

in which :

Y and Z ¹ and Z ² have the definitions given above;

- a = 1 or 2, b = 0, 1 or 2 and a + b = 2 or 3

- c = 1 or 2.

Particularly preferably, the organopolysiloxanes (B) are chosen from organopolysiloxanes comprising units (1.1) selected from the group consisting of Si0 ₂ YZ ^1/2 and SiO ₂ YZ ^_1/2 units and (I.2) selected from the group consisting of Z ² ₂ Si0 _{_2/2} and Z ² ₃ SiO _{/ 2,} Y, Z ¹ and Z ² are as defined above, provided that the polyorganosiloxane (B) comprises, per molecule, at least a siloxyl unit (1.1) bearing at least one functional group of formula (I.3) defined above.

Preferably, the organopolysiloxanes (B) have a degree of polymerization of between 2 and 5000, preferably between 2 and 1500, more preferably between 2 and 500.

Preferably, the organopolysiloxanes (B) comprise a number of siloxyl units (1.1) of between 1 and 100, preferably between 2 and 80.

Preferably, the organopolysiloxanes (B) comprise an amount of NH / gram bond of between 1 .10 ⁵ and 1 .10 ¹ mol / g, and preferably between ⁵ × 10 ^-5 and ⁵ × 10 ^-2 mol / g.

Preferably, the organopolysiloxanes (B) may be chosen from compounds of formula:

preferably 1 to 800 (IV) with I = 1 to 1000, preferably 1 to 800 and m = 1 to 150, preferably 1 to 100;

(V) with n = 1 to 1000, preferably 1 to 800

1 to 150, preferably 1 to 100;

preferably 1 to 800.

According to another embodiment, the organopolysiloxane (B) may be chosen from the compounds of formula (IV) and (V) as described above with end units dimethylmethoxysilyl or dimethylethoxysilyl instead of trimethylsilyl.

In a particular embodiment, the organopolysiloxane (B) may be in emulsion. All of the preferred characteristics defining the organopolysiloxanes (B) can be combined with one another. In a general way, it is possible to define the ratio r representing the ratio between the number of moles of alkene or alkyne function of the compound (C) of which at least one of the substituents is an electron-withdrawing group or an acid function, preferably the number of moles of C = C or C≡C double bonds in which at least one of the substituents is an electron-withdrawing group or an acid function, and the number of moles of NH bonds carried by the organopolysiloxane (B). The ratio r corresponds to the following relation: n (C = C, C≡C)

r =

n (N - H) It is also possible to define the ratio J representing the ratio between the number of moles of acid functions of the compound (C) and the number of moles of amine functional groups of the organopolysiloxane (B). The ratio J corresponds to the following relationship: number of moles of the compound (C) x number of acid functions of the compound (C)

number of moles of the compound (Z?) x number of amine functions of the compound (B)

By amine function is meant primary or secondary amines. It should therefore be understood that one mole of primary amine function contains two moles of N-H bonds and one mole of secondary amine function contains one mole of N-H bonds.

Preferably, the ratio J is between 0.01 and 20, preferably between 0.5 and 3 and even more preferably between 0.5 and 1.5.

Preferably, the ratio r is between 0.01 and 10, preferably between 0.05 and 2, and even more preferably between 0.2 and 1.5.

Preferably, the ratio J is between 0.01 and 20, preferably between 0.5 and 3, more preferably between 0.5 and 1.5, and the ratio r is between 0.01 and 10, preferably between 0.05 and 2 and even more preferably between 0.2 and 1.5.

Preferably, the organopolysiloxane (B) has a dynamic viscosity measured at 25 ° C. with an imposed stress rheometer, especially TA-DHRI1, of between 1 and 100,000 mPa.s, preferably between 100 and 50,000 mPa.s. .

Particularly advantageously, by the method used, the organopolysiloxane (A) has a dynamic viscosity measured at 25 ° C, with an imposed stress rheometer, especially TA-DHRIl, at least 10 times greater than that of organopolysiloxane (B).

The organopolysiloxane (A) may optionally be in the form of an emulsion. The organopolysiloxanes (A) obtained may be viscoelastic liquids or viscoelastic solids. One can speak of gel when the organopolysiloxane (A) is at the transition between a liquid and a viscoelastic solid. It is thus possible to obtain organopolysiloxanes (A) having modulable viscoelastic properties.

The present invention also relates to a process for preparing an organopolysiloxane (A) comprising contacting, at a temperature of between 10 and 75 ° C, between: at least one compound (C) chosen from organic compounds comprising at least one alkene or alkyne function of which at least one of the substituents is an acid function and organic compounds comprising at least one acid function and at least one alkene function or alkyne of which at least one of the substituents is an electron-withdrawing group; and at least one acid function, and

at least one organopolysiloxane (B) comprising siloxyl units (1.1) and (I.2) of the following formulas:

There _is ¾si¾ ^ z _c ² sio ^

² (M); ² (i.2)

in which :

- a = 1 or 2, b = 0, 1 or 2 and a + b = 1, 2 or 3

- c = 1, 2, 3 or 4

-E- (NH-G) _h - (NH ₂ ) i (I.3)

in which :

- h = 0 or 1;

i = 0 or 1;

- h + i = 1 or 2

the symbols Z ¹ and Z ² , which are identical or different, represent a monovalent hydrocarbon radical having from 1 to 30 carbon atoms and optionally comprising one or more unsaturations and / or one or more fluorine atoms, a hydroxyl group, or a radical; -OR ¹ with R ¹ represents a hydrocarbon radical -C ₁₀ linear, cyclic or branched, and preferably Z ¹ and Z ² represent a monovalent hydrocarbon group selected from the group consisting of alkyl groups having 1 to 8 carbon atoms , alkenyl groups having 2 to 6 carbon atoms and aryl groups having 6 to 12 carbon atoms optionally comprising one or more fluorine atoms, a hydroxyl group, or a radical-OR ¹ with R ¹ which represents a radical C ₁ -C ₁₀ linear hydrocarbon, cyclic or branched, and even more preferentially selected from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, vinyl, hydroxyl, ethoxyl, methoxyl, xylyl, tolyl and phenyl;

According to a variant of the process, the compound (C) and the organopolysiloxane (B) are brought into contact at a temperature strictly below 10 ° C., so as to avoid heating up the reaction medium, and the temperature of the reaction medium is then brought gradually at a temperature between 10 and 75 ° C.

Without wishing to be bound by any theory, the process of the present invention resulted in an Aza-Michael reaction between the NH bonds carried by the organopolysiloxane (B) and the alkene or alkyne functions of the compound (C). Since the compound (C) also comprises at least one acidic function, the process of the invention also implements an acid-base reaction generating ionic bonds between the amine functions of the organopolysiloxane (B) and said acid functions of the compound ( VS). These ionic bonds confer on the organopolysiloxane (A) a supramolecular character. When the process is carried out at temperatures above 75 ° C, reactions may lead to the formation of undesired products.

In a particularly advantageous manner, the combination of these two reactions makes it possible to obtain an organopolysiloxane (A) whose viscosity, measured at 25 ° C., with an imposed stress rheometer, especially TA-DHRII, at least 10 times greater than that organopolysiloxane (B).

According to the various implementations of the process of the invention (choice of organopolysiloxane (B), choice of reaction conditions (reaction time, temperature, ratio of reagents, etc.)), the organopolysiloxane (A) obtained can be a viscoelastic liquid or a viscoelastic solid. One can speak of gel when the organopolysiloxane (A) is at the transition between a liquid and a viscoelastic solid. It is thus possible to obtain organopolysiloxanes (A) having modulable viscoelastic properties.

In the context of the present invention, the term "Aza-Michael reaction" is understood to mean the amine addition reaction on carbon-carbon multiple bonds, in particular alkene or alkyne function, and more preferentially carbon-carbon double bonds.

The compound (C) and the organopolysiloxanes (B) and (A) are as defined above. The duration of the contacting between the compound (B) and the compound (C) is variable, between a few minutes or a few hours and several days. It depends on the nature of the compounds (B) and (C) as well as the temperature at which they are brought into contact. The Man in the art will adapt this period, especially following the progress of the reaction by analytical methods such as ¹ H NMR

The organopolysiloxane (B) can be obtained by reaction between an organopolysiloxane comprising at least one hydroxyl group and an alkoxysilane comprising at least one functional group of formula (I.3) as described above.

According to one embodiment of the process according to the invention, the organopolysiloxane (B) can be prepared in situ in the presence of the compound (C).

Preferably, the process of the present invention is carried out at a temperature between 10 and 70 ° C, preferably between 15 and 70 ° C.

According to a preferred embodiment, the process of the invention is carried out at atmospheric pressure.

The process can be carried out in the presence of microwave and / or ultrasonic irradiation. The process according to the invention can be carried out under air but also under an inert gas atmosphere such as argon or nitrogen.

Particularly advantageously, the process of the present invention can be carried out in bulk or in the presence of a solvent. The solvent is in particular chosen from:

protic polar solvents, such as, for example, water, alcohols, ionic liquids;

apolar solvents such as, for example, heptane, toluene, methylcyclohexane;

aprotic polar solvents such as ketones (for example acetone), ethers, esters, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), dimethylformamide (DMF).

Preferably, the process of the invention is carried out in the absence of solvent (in bulk). The process of the present invention may be carried out in the presence of a catalyst, especially chosen from basic, acidic, nucleophilic or organometallic catalysts. The method of the invention can also be implemented in the presence of a load. In the context of the present invention, the fillers are preferably mineral. They can be especially siliceous. As for siliceous materials, they can act as reinforcing or semi-reinforcing filler. The reinforcing siliceous fillers are chosen from colloidal silicas, silica powders for combustion and precipitation, or mixtures thereof. These powders have an average particle size generally less than 0.1 μηι (micrometers) and a BET specific surface area greater than 30 m ² / g, preferably between 30 and 350 m ² / g. Semi-reinforcing siliceous fillers such as diatomaceous earth or ground quartz can also be used. In the case of non-siliceous mineral materials, they can be used as semi-reinforcing mineral filler or stuffing. Examples of these non-siliceous fillers that can be used alone or in a mixture are carbon black, titanium dioxide, aluminum oxide, hydrated alumina or aluminum trihydroxide, expanded vermiculite, unexpanded vermiculite, calcium carbonate optionally surface-treated with fatty acids, zinc oxide, mica, talc, iron oxide, kaolin, barium sulphate and slaked lime. These fillers have a particle size generally between 0.001 and 300 μηι (micrometers) and a BET surface area of less than 100 m ² / g. In a practical but nonlimiting manner, the fillers used may be a mixture of quartz and silica. Charges can be processed by any suitable product.

The filler may be introduced either directly mixed with the organosiloxane (B) or in the reaction medium after mixing the organosiloxane (B) and the compound (C).

In terms of weight, it is preferable to use a loading quantity of between 1% and 50% by weight, preferably between 1% and 30% by weight relative to all the constituents (B) and (C) and even more preferably from 1% to 10% by weight relative to all the constituents (B) and (C).

Preferably, in the context of the process of the present invention, the ratio J, as defined above, is between 0.01 and 20, preferably between 0.5 and 3 and even more preferably between 0.5 and 1. 5. Preferably, in the context of the process of the present invention, the ratio r, as defined above, is between 0.01 and 10, preferably between 0.05 and 2, and even more preferably between 0.2 and 1, 5.

Preferably, in the context of the process of the present invention the ratio J, as defined above, is between 0.01 and 20, preferably between 0.5 and 3, even more preferentially between 0.5 and 1. , And the ratio r, ratio r is between 0.01 and 10, preferably between 0.05 and 2 and even more preferably between 0.2 and 1.5.

The present invention also relates to a composition K1 comprising at least one organopolysiloxane (A) according to the invention. Preferably, the composition K1 may be an organopolysiloxane composition. The composition K1 may further comprise at least one filler and / or at least one organopolysiloxane.

The composition K1 may also comprise one or more usual functional additives. As families of usual functional additives, mention may be made of:

silicone resins;

adhesion promoters or modulators;

additives to increase consistency;

the pigments,

additives for heat resistance, resistance to oils or fire resistance, for example metal oxides.

The composition K1 may also comprise an organopolysiloxane comprising at least one carboxylic function.

The composition K1 may also comprise at least one organopolysiloxane (B) as defined above.

Particularly advantageously, as specified above, the organopolysiloxane (A) has a higher dynamic viscosity than the starting organopolysiloxane (B). As a result, these organopolysiloxanes (A) can be used in the same applications as silicone elastomers, or in the same applications as silicone gels, for example for woundcare (coating coating, manufacture of external prostheses, anti-mold cushions). scarres), or for the encapsulation of electronic components or as coatings, in particular for the coating of flexible films made of paper or plastic as well as for the textile coating (airbag).

The organopolysiloxanes (A) can also be used as additives and especially as additive adhesion promoters, anti-fog, antifoam, antistatic, antibacterial, anti-corrosion, anti-fire, anti graffiti or for temporary printing, for thin film coating, or in different compositions.

By way of nonlimiting illustration, these organopolysiloxanes (A) and the compositions K1 comprising them can be used in various applications such as paints, coatings, adhesives, sealants, personal care, health care, textile treatment electronics, automobiles, rubbers, anti-foam compositions, etc.

The present invention also relates to a composition X for the preparation of an organopolysiloxane (A) according to the invention, comprising:

There _is ¾si¾ ^ z _c ² sio ^

² (M); ² (i.2)

in which :

- a = 1 or 2, b = 0, 1 or 2 and a + b = 1, 2 or 3

- c = 1, 2, 3 or 4

-E- (NH-G) _h - (NH ₂ ) i (I.3)

in which :

- h = 0 or 1;

i = 0 or 1;

- h + i = 1 or 2

the symbols Z ¹ and Z ² , which are identical or different, represent a monovalent hydrocarbon radical having from 1 to 30 carbon atoms and optionally comprising one or several unsaturations and / or one or more fluorine atoms, a hydroxyl group, or a radical-OR ¹ with R ¹ which represents a linear, cyclic or branched C1-C10 hydrocarbon radical, and preferably Z ¹ and Z ² represent a monovalent hydrocarbon group selected from the group consisting of alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 6 carbon atoms and aryl groups having 6 to 12 carbon atoms optionally comprising one or more atoms of fluorine, a hydroxyl group, or a radical-OR ¹ with R ¹ which represents a linear, cyclic or branched C1-C10 hydrocarbon radical, and even more preferentially chosen from the group consisting of a methyl, ethyl and propyl group, 3,3-trifluoropropyl, vinyl, hydroxyl, ethoxyl, methoxyl, xylyl, tolyl and phenyl;

The compound (C) and the organopolysiloxanes (A) and (B) being as defined above.

The present invention will now be described by way of non-limiting examples. Examples

In the examples below, given for illustrative purposes, reference is made to the following definitions:

Mn represents the average molar mass in number.

PDMS = polydimethylsiloxane

The PDMSs implemented in the examples which follow correspond to one of the following formulas:

- ORGANOSILOXANE (1):

N- (2-aminoethyl) -3-aminopropylméthylbis (trimethylsiloxy) silane

- ORGANOSILOXANE (2): Commercial, Gelest SIA0604.5

3-aminopropylméthylbis (trimethylsiloxy) silane,

PDMS (3): Gelest, Mn = 3000 g / mol; compound of formula (III); amount of N-H bond per gram = 1.33 × 10 ³ mol / g;

- PDMS (4): Gelest; compound of formula (III) NH linkage amount per gram = 8.0 × 10 ^-5 mol / g; Mn = 50000G / mol

- PDMS (5): Gelest; compound of formula (III) Mn = 30000g / mol; amount of NH bond per gram = 1, 33.10 ⁴ mol / g

PDMS (6): Gelest; compound of formula (IV) NH linkage amount per gram = 1.71 .10 ^-3 mol / g;

- PDMS (7): Gelest; compound of formula (IV); amount of NH bond per gram = 2.43 × 10 ^-3 mol / g; - PDMS (8): Gelest; compound of formula (IV); amount of NH bond per gram = 5.14 × 10 ^-3 mol / g;

- PDMS (9): Gelest; compound of formula (V) NH linkage amount per gram = 6.54 × 10 ^-3 mol / g;

PDMS (10): Gelest; Compound of formula (V); amount of NH bond per gram = 8.57 × 10 ^-4 mol / g; - PDMS (1 1): Bluestar Silicones; compound of formula (V) NH linkage amount per gram = 3.21 .10 ⁴ mol / g;

- PDMS (12): Bluestar Silicones; compound of formula (V) with dimethylmethoxysilyl end units in place of trimethylsilyl, amount of NH bond per gram = 1.61 .10 ^-4 mol / g

Dynamic viscosity:

The dynamic viscosity of the products was measured using an imposed stress rheometer (TA-DHRII). The measurements were made in flow mode with a cone / plane geometry of 40 mm diameter and having a truncation of 52 μηι. Viscosity was recorded as a function of shear rate (0.01-100 s ^-1 ) at 25 ° C.

NMR:

¹ H nuclear magnetic resonance (NMR) spectra were recorded on a 400 MHz Bruker Avance III spectrometer. The samples were dissolved either in deuterated chloroform or in a CDCl ₃ / MeOD (60/40 mol) mixture and analyzed at 27 ° C.

Rheology:

The rheological analyzes were performed using an imposed stress rheometer (TA-DHRII) at 25 ° C using a plane / plane geometry (40 mm diameter). Frequency sweeps were recorded in the linear viscoelastic range of products between 100 and 0.01 Hz. EXAMPLE 1 Preparation of Organosiloxane (1)

ORGANOSILOXANE (1) was prepared according to the following protocol:

N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (5.0 g) and hexamethyldisiloxane (20.1 g) were mixed in a two-necked flask topped with a condenser in the presence of tetramethylammonium hydroxide dissolved in the reaction medium. methanol (0.5 g). The reaction mixture was stirred under nitrogen flushing at room temperature for 10 minutes and then heated at 90 ° C for 2 hours and then at 130 ° C for 30 minutes. The reaction mixture was then cooled to room temperature (20 to 25 ° C) and the obtained product was purified by fractional distillation under vacuum. A fraction of 2.3 g corresponding to ORGANOSILOXANE (1) was removed at 106 ° C. at 0.41 mbar at the top of the column, the boiler being heated to 200 ° C. The reaction yield is 30%.

EXAMPLE 2 Reaction of Organosiloxane (1) with Acrylic Acid

In a two-colored balloon, ORGANOSILOXANE (1) and acrylic acid are mixed. ORGANOSILOXANE (1) and acrylic acid are added in amounts such that r = 0.33 and J = 0.5. The mixture is stirred magnetically for 24 h at 50 ° C at atmospheric pressure.

A of the reaction medium ¹ H NMR analysis taken at 1, 4, 6, 8 and 24 hours of reaction, has shown the disappearance of acrylic functions over time. Without wishing to be bound by any theory, this disappearance of the acrylic functions is due to the Aza-Michael reaction between the NH bonds of ORGANOSILOXANE (1) and the acrylic functions.

A test 3 was also performed identical to test 2 (same proportion) but replacing the organosiloxane (1) with octamethyltrisiloxane. This test did not show the formation of an acrylic acid polymer. This shows that the disappearance of the acrylic functions observed by NMR under test 2 is not due to a polymerization reaction of acrylic acid but to the reaction of Aza-Michael between the NH bonds borne by ORGANOSILOXANE. (1) and the carbon-carbon double bond of acrylic acid.

Example 3 Influence of the Temperature on the Conversion of Acrylic Acid

In three sealed pillboxes were mixed ORGANOSILOXANE (2) and acrylic acid (r = 0.5, J = 1). The reaction mixtures are maintained at a temperature of 25 ° C. (Test 5), 50 ° C. (Test 6) and 70 ° C. (Test 7). The conversion of acrylic functions to The course of time was followed by ¹ H NMR. The results are shown in the following Table 1.

Table 1

These results show that an increase in the temperature makes it possible to obtain a total conversion of the acrylic functions as early as 7h at 70.degree.

The products obtained were analyzed qualitatively in terms of viscosity, homogeneity, solubility, etc. The results show that the products obtained are homogeneous, soluble in chloroform, dispersible in water, more viscous than the starting ORGANOSILOXANE (2) and have a transparency equivalent to that of the starting ORGANOSILOXANE (2).

EXAMPLE 4 Reaction of PDMS (3) with Acrylic Acid in Mass

In a single-necked 15mL flask, the PDMS (3) and acrylic acid were mixed. PDMS (3) and acrylic acid are added in amounts such that r = 0.5 and J = 1. The reaction mixture was stirred magnetically for 72 hours at a temperature of 50 ° C. No post-reaction treatment was applied. ¹ H NMR analysis of the product obtained in CDCl ₃ at 27 ° C. (128 scans) made it possible to show a disappearance of the acrylic functions. The conversion was calculated on the basis of ¹ H NMR at 96% at t = 72 h. The dynamic viscosities of PDMS (3), PDMS (3) and acrylic acid at t = 0, and the product obtained after 72 hours of reaction were measured at different shear rates (0.1-100 s ^-1 ). and are presented in Table 2 below.

Table 2

These results show that the PDMS (3) initially has a low viscosity. Dynamic viscosity increases when PDMS (3) is mixed with acrylic acid at t = 0. Without wishing to be bound by any theory, this increase in dynamic viscosity is due to the acid-base reaction between the amine functions of PDMS (3) and acrylic acid. The dynamic viscosity of the final product (product resulting from the Aza-Michael reaction between PDMS (3) and acrylic acid after 72 hours) is more than 100 times higher than that of PDMS (3) and much higher than that PDMS (3) and acrylic acid at t = 0. Without wishing to be bound by any theory, and as shown by the results of Example 3, this increase in dynamic viscosity is due to the Aza-Michael reaction coupled to an acid-base reaction between the PDMS (3) and acrylic acid.

Example 5: Variation of the nature of PDMS, J and r

PDMSs 4 to 11 and acrylic acid were reacted in bulk, in the ratios described in Table 4 below, in a suitable plastic container. The reaction mixture was homogenized using a high speed planetary mixer (2750 rpm) for 2 minutes and 30 seconds. An exothermic reaction is visible during homogenization, which is why the products have been cooled to -20 ° C. before being homogenized. Thus, the maximum temperature within the product does not exceed 25 ° C. After homogenization, the products are left at room temperature for several days (> 17 days). The reaction conditions for the various tests are collated in the following Table 3. N ° TEST PDMS r J

PDMS (4) 0.52 1

11 PDMS (5) 0.54 1

12 PDMS (6) 0.50 1

13 PDMS (7) 0.51 1

14 PDMS (8) 0.50 1

PDMS (9) 0.67 1

16 PDMS (10) 0.68 1

17 PDMS (10) 1, 35 2

18 PDMS (1 1) 0.71 1

Table 3

The products obtained were analyzed by ¹ H NMR after 17 days of reaction at ambient temperature (20-25 ° C.), which made it possible to calculate the conversion of the acrylic functions. The products obtained were also evaluated in terms of viscosity (visual observation) and solubility in different solvents. The results of these analyzes are summarized in Table 4 below.

Table 4 Legend:

S: soluble; I: insoluble; D: dispersible; -: not tested

CDCl ₃ : Deuterated chloroform; H ₂ O: water; IPA: Isopropanol; THF Tetrahydrofuran MCH: Methylcyclohexane The products obtained all have a viscosity at least 10 times greater than the respective starting PDMSs. A high conversion rate of acrylic functions after 17 days was determined by ¹ H NMR for all products that can be solubilized in deuterated chloroform. The variation in the nature of the PDMS and the ratios r and J therefore makes it possible to adjust the properties of the synthesized materials.

The viscoelastic properties of the products obtained for tests 16, 17 and 18 were recorded using an imposed stress rheometer. Initial viscoelastic properties of PDMS (10) and PDMS (11) were also measured. For this, the evolution of the elastic (G ') and viscous (G ") modules as a function of frequency has been recorded under the following conditions:

Deformation (δ) of 0.1% applied for test 16 and PDMS (10), strain (δ) of 0.03% applied for test 17 and strain (δ) of 0.2% applied for test 18 and the PDMS (1 1).

The results obtained after 18 days of reaction are grouped in the following two tables 5 and 6.

Table 5

Table 6

The results show that the crossing point G '/ G "is at 0.2 Hz for test 16, at 0.1 Hz for test 17 and at 0.6 Hz for test 18. The three products thus, they behave like viscoelastic solids over a wide frequency range.

The results also show an increase in the viscosity of the products obtained in tests 16 and 17 with respect to PDMS (10) and in test 18 relative to PDMS (1 1), this increase being due to the Aza reaction. -Michael coupled to the acid-base reaction.

From these results it was possible to deduce, by calculation, the complex viscosities presented in the following Tables 7 and 8.

Table 7 No. TEST PDMS (11) 18

Frequency (Hz) η * (Pa.s)

1 00 7 2.0.1 0 ²

1 0 1 1 1, 6.1 0 ³

1 1 2 9,0.1 0 ³

0.1 1 3 3.6.1 0 ⁴

0.01 1 5 1, 0.1 0 ⁵

Table 8

The results show a decrease in the complex viscosity as the frequency increases.

Example 6: Reaction of PDMS (3) with Acrylic Acid in the Presence of a Solvent (25 ° C.) In a 25 ml monocolumn flask, PDMS (3), isopropanol (IPA, 33%) are mixed by weight relative to the total weight of PDMS (3) and acrylic acid) and acrylic acid. PDMS (3) and acrylic acid are added in amounts such that r = 0.5 and J = 1. The reaction mixture is stirred magnetically at 25 ° C for 7 days. ¹ H NMR analysis of the product obtained in CDCl ₃ at 27 ° C. (128 scans) made it possible to show the disappearance of the acrylic functions. At t = 42 h the conversion was estimated on the basis of ¹ H NMR at 37%.

Example 7: Influence of the solvent (50 ° C.)

The reaction involves the PDMS (3) and the acrylic acid used in Examples 5 and 7 in the same proportions (r = 0.5, J = 1). To the reaction medium is added or not a solvent (85 mol%): tert-butanol, isopropanol / water solution (50/50 mol) or saturated solution of ammonia / isopropanol and the mixture is stirred with magnetic stirring at 50 ° C. C for 24h. The conversion of acrylic functions is followed by ¹ H NMR and the results are shown in Table 9 below. Conversion (%) based

No. TEST Reaction medium of time (h)

0 h 1 h 4 h 8 h 24 h

9 In mass 0 8 1 7 31 69

19 Tert-Butanol 0 5 1 2 25 64

20 IPA / Water 0 0 3 5 35

21 Ammonia solution 0 8 1 8/56

Table 9

These data show, in combination with the results of Examples 2, 4 and 6, that the process of the invention can be carried out in the presence of different solvents or in bulk.

EXAMPLE 8 Reaction of Organosiloxane (2) with 2-Carboxyethylacrylate

In a sealed pill organizer were mixed ORGANOSILOXANE (2) and 2-carboxyethyl acrylate in proportions such that r = 0.5 and J = 1. The mixture is stirred magnetically for 48 h at 50 ° C at atmospheric pressure. A of the reaction medium ¹ H NMR analysis taken at 1, 4, 7, 24 and 48 hours of reaction, has shown the disappearance of acrylic functions over time. Without wishing to be bound by any theory, this disappearance of the acrylic functions is due to the Aza-Michael reaction between the NH bonds of the organosiloxane (2) and the acrylate functions. At t = 48h, a conversion of the acrylate functions of a value of 96% is reached. Table 10 below groups the data in terms of conversion versus reaction time.

Table 10 Example 9: Effect of the process temperature. Reaction between an orqanopolysiloxane (PDMS 12) and itaconic acid.

PDMS (12) is an organopolysiloxane of the same overall formula as compound (V) but with terminal dimethylmethoxysilyl units instead of trimethylsilyl, and having a quantity of NH bonds per gram of 1. 61 ⁴ mol / g.

Two reactions were carried out, one at 50 ° C according to the invention and one at 120 ° C (comparative test). Itaconic acid is a solid that is not soluble in PDMS (12) at room temperature (20-30 ° C). It was previously solubilized in methanol.

Example 9-a

0.1 g of itaconic acid solubilized in 0.23 g of methanol, ie 0.008 mol of itaconic acid, which corresponds to 0.0016 mol of acid function, were mixed with 15.00 g of PDMS (12) as described above, which corresponds to 0.0024 mol of NH bonds and 0.0016 mol of amine functions. The PDMS (12) was previously cooled to below 0 ° C prior to the addition of the solubilized itaconic acid. The mixture was then homogenized with a planetary mixer for 5 minutes at 2750 rotations per minute, the maximum temperature within the mixture not exceeding 25 ° C. After homogenization, the mixture was placed in an oven at a temperature of 50 ° C for one week so that the reaction of aza-Michael and the methanol is gradually evaporated.

The product obtained is colorless, transparent, homogeneous and soluble in THF and methylcyclohexane.

Example 9-b

0.1 g of itaconic acid solubilized in 0.23 g of methanol, ie 0.008 mol of itaconic acid, which corresponds to 0.0016 mol of acid function, were mixed with 15.00 g of PDMS (12) as described above, which corresponds to 0.0024 mol of NH bonds and 0.0016 mol of amine functions. The reaction medium is placed for 4 hours at 120 ° C. in a monocolumn flask surmounted by a refrigerant.

The product obtained is slightly yellowish and is not soluble in THF or in methylcyclohexane.

The two products obtained do not have the same properties which shows that they are different. Example 10 Synthesis of a Supramolecular Material

0.77 g of acrylic acid, ie 0.01 moles of acid function, were mixed with 100 g of PDMS (12) previously cooled to -20 ° C., having a structure as described in Example 10, which corresponds to 0.0161 mol of NH bonds and 0.01 1 mol of amine functions (r = 0.68 and J = 1). The mixture was then homogenized using a planetary mixer for 5 minutes at 2750 rpm, the maximum temperature within the mixture not exceeding 25 ° C. After homogenization, the mixture was placed in an oven in an airtight bottle at a temperature of 50 ° C for one week.

The product obtained is a transparent viscoelastic solid. This product swells in THF and methylcyclohexane. After addition of a chaotropic agent (<1% mass) which makes it possible to break the ionic bonds within the material, the product is totally soluble thus showing its supramolecular character.

The supramolecular product obtained was also converted into a 1 mm thick film under pressure for 48 hours at 50 ° C. Specimens of the type H3 (L ₀ = 17mm, thickness 1 mm, width = 4mm according to ISO 37: 201 1) are die-cut and left for one day at 45% ± 5% humidity. and at 25 ° C ± 1 ° C. Uniaxial tensile tests or cyclic tensile tests were carried out with an MTS 2 / m tensile machine with a 10N sensor and at a pulling speed of 0.25s- ¹ . The dependence of the mechanical properties with the speed The drawing was carried out by varying the drawing speed from 0.08 s-1 to 0.42 s-1, the tensile strength obtained is around 0.2 MPa and the elongation at break is extremely high. of the order of 4000% Example 1 1: Synthesis of a charged supramolecular material

Example 10 was redone as previously described. Directly after homogenization of the two compounds with the aid of the planetary mixer, 5% by weight of a hydrophobic fumed silica (Aerosil® R104) was added and this mixture is again homogenized using the planetary mixer for 10 minutes at room temperature. 2750 rpm then placed in an oven in an airtight bottle at a temperature of 50 ° C for one week.

As described above, specimens H3 were cut from the product obtained, previously put into film form. Tensile tests were performed as in Example 1 1. The tensile strength is 0.5 MPa and the elongation at break is still very high, of the order of 2000%.

Claims

1. Organopolysiloxane (A) obtainable by reaction, at a temperature of between 10 and 75 ° C., between:

¾¾SiQ ^ (a + b) Z _c ² SiO 4-c

(1.1) ² (I.2)

in which :

- a = 1 or 2, b = 0, 1 or 2 and a + b = 1, 2 or 3

- c = 1, 2, 3 or 4

the symbols Y, which are identical or different, represent a functional group of formula

(I.3):

-E- (NH-G) _h - (NH ₂ ) i (I.3)

in which :

- h = 0 or 1;

i = 0 or 1;

- h + i = 1 or 2

the symbols Z ¹ and Z ² , which are identical or different, represent a monovalent hydrocarbon radical having from 1 to 30 carbon atoms and optionally comprising one or more unsaturations and / or one or more fluorine atoms, a hydroxyl group, or a radical; -OR ¹ with R ¹ represents a hydrocarbon radical in C1-C1 ₀ linear, cyclic or branched, and preferably Z ¹ and Z ² represent a monovalent hydrocarbon group selected from the group consisting of alkyl groups having 1 to 8 carbon of carbon, alkenyl groups having 2 to 6 carbon atoms and aryl groups having from 6 to 12 carbon atoms optionally comprising one or more fluorine atoms, a hydroxyl group, or an OR ¹ radical with R ¹ which represents a linear, cyclic or branched C1-C10 hydrocarbon radical, and even more preferably chosen from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, vinyl, hydroxyl, ethoxyl, methoxyl, xylyl, tolyl and phenyl;

Organopolysiloxane (A) according to claim 1 wherein the temperature is between 10 and 70 ° C and preferably between 15 and 70 ° C.

3. Organopolysiloxane (A) according to claim 1 or 2, wherein the compound (C) is selected from organic compounds comprising at least one carbon-carbon double bond of which at least one of the substituents is a carboxylic acid function.

The organopolysiloxane (A) according to claim 1 to 3, wherein the compound (C) is selected from the compounds of formula

in which :

R ² , R ³ and R ⁴ , which may be identical or different, represent a hydrogen atom, a COOH group or a C ₁ to C ₆ , preferably C ₁ to C ₃ , alkyl group, preferably methyl; R ⁵ represents a hydrogen atom, an alkyl group or an aryl group, wherein the alkyl and aryl comprise at least one COOH group.

5. Organopolysiloxane (A) according to one of claims 1 to 4, wherein the compound (C) is selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, 2-carboxyethylacrylate , 3-carboxypropylacrylate, maleic acid, fumaric acid, 2- (acryloyloxy) acetic acid, 2- (acryloyloxy) propanoic acid, 3- (acrylolyloxy) propanoic acid, acid 2 2- (acryloyloxy) -2-phenylacetic acid, 4- (acryloyloxy) butanoic acid, 2- (acryloyloxy) -2-methylpropanoic acid, 5- (acryloyloxy) pentanoic acid, (E) -but -2-enoic, (Z) -prop-1-ene-1,2,3-tricarboxylic acid, cinnamic acid, sorbic acid, 2-hexenoic acid, 2-pentenoic acid, 2,4-pentadienoic acid, ethenesulfonic acid, vinylphosphonic acid, (1-phenylvinyl) phosphonic acid, 3- (vinylsulfonyl) propanoic acid, 2- (vinylsulfonyl) acetic acid, 2- (vinylsulfonyl) succinic acid, acetylene dicarboxylic acid and propiolic acid.

6. Organopolysiloxane (A) according to one of claims 1 to 5, wherein the organopolysiloxane (B) is selected from organopolysiloxanes comprising siloxyl units (1.1) and (I.2) of the following formulas:

There _is ¾si¾ ^ z _c ² sio ^

² (M); ² (i.2)

in which :

Y and Z ¹ and Z ² are as defined in claim 1;

- a = 1 or 2, b = 0, 1 or 2 and a + b = 2 or 3

- c = 1 or 2.

Organopolysiloxane (A) according to one of claims 1 to 6, characterized in that the organopolysiloxane (B) has a degree of polymerization of between 2 and 5000, preferably between 2 and 500.

8. Organopolysiloxane (A) according to one of claims 1 to 7, wherein the organopolysiloxane (B) has a dynamic viscosity measured at 25 ° C with an imposed stress rheometer of between 1 and 100 000 mPa.s, preferably between 100 and 50,000 mPa.s.

9. Organopolysiloxane (A) according to any one of claims 1 to 8, characterized in that its viscosity, measured at 25 ° C with an imposed stress rheometer, is at least 10 times greater than that of the organopolysiloxane (B ).

A process for preparing an organopolysiloxane (A) comprising contacting, at a temperature between 10 and 75 ° C, between:

at least one compound (C) chosen from organic compounds comprising at least one alkene or alkyne function of which at least one of the substituents is an acid function and organic compounds comprising at least one acid function and at least one alkene function or alkyne of which at least one of the substituents is an electron-withdrawing group, and

at least one organopolysiloxane (B) chosen from organopolysiloxanes comprising siloxyl units (1.1) and (I.2) of the following formulas: There _is ¾si¾ ^ z _c ² sio ^

² (M); ² (i.2)

in which :

- a = 1 or 2, b = 0, 1 or 2 and a + b = 1, 2 or 3

- c = 1, 2, 3 or 4

-E- (NH-G) _h - (NH ₂ ) i (I.3)

in which :

- h = 0 or 1;

i = 0 or 1;

- h + i = 1 or 2

1 1. Process according to Claim 9, carried out at a temperature of between 10 and 70 ° C and preferably between 15 and 70 ° C.

12. Method according to any one of claims 10 or 1 1, implemented in bulk or in the presence of a solvent, in particular selected from aprotic, aprotic, polar polar protic solvents.

13. Process according to any one of claims 10 to 12, in which the organopolysiloxane obtained (A) has a dynamic viscosity, measured at 25 ° C. with an imposed stress rheometer, at least 10 times greater than that of the organopolysiloxane (B).

The process according to any one of claims 10 to 13, wherein the ratio r represents the ratio between the number of moles of alkene or alkyne function of the compound (C) of which at least one of the substituents is an electron-withdrawing group or an acid function, and the number of moles of NH bonds carried by the organopolysiloxane (B)

n (C = C or C≡ C)

Γ ^~ n (N - H)

is between 0.01 and 10, preferably between 0.05 and 2 and even more preferably between 0.2 and 1.5.

The process according to any one of claims 10 to 14, wherein the ratio J represents the ratio of the number of moles of acid functions of the compound (C) to the number of moles of amine function of the organopolysiloxane (B). number of moles of the compound (C) x number of acid functions of the compound (C)

the number of moles of the compound (Z 2) x number of amine functions of the compound (B) is between 0.01 and 20, preferably between 0.5 and 3, even more preferably between 0.5 and 1.5.

16. Composition K1 comprising at least one organopolysiloxane (A) according to one of claims 1 to 9, and optionally at least one filler and / or at least one other organopolysiloxane and / or one or more usual functional additives, in particular chosen from silicone resins, adhesion promoters or modulators, additives for increasing the consistency, pigments, heat resistance, oil-resistance or fire-resistance additives and / or an organopolysiloxane comprising at least one carboxylic function and / or at least one organopolysiloxane (B) as defined in claims 1, 6, 7 or 8.

17. Use of at least one organopolysiloxane (A) according to one of claims 1 to 9, or a composition K1 according to claim 16, in the woundcare, for example coating of dressings, manufacture of external prostheses, cushions anti -escars; for the encapsulation of electronic components; as coatings, in particular for the coating of flexible films of paper or plastic; for textile coating; as additives, and especially as additives promoting adhesion, anti-fog, antifoam, antistatic, antibacterial, anti-corrosion, anti-fire, anti graffiti; for temporary printing, or for thin film coating.

18. Use of at least one organopolysiloxane (A) according to one of claims 1 to 9, or a composition K1 according to claim 16 in paints, coatings, adhesives, mastics, personal care, health care, textile processing, electronics, automobiles, rubbers, anti-foam compositions.

19. Composition X for the preparation of an organopolysiloxane (A) according to one of claims 1 to 9, comprising:

There _is ¾si¾ ^ z _c ² sio ^

² (M); ² (i.2) in which:

- a = 1 or 2, b = 0, 1 or 2 and a + b = 1, 2 or 3

- c = 1, 2, 3 or 4

-E- (NH-G) _h - (NH ₂ ) i (I.3) in which :

- h = 0 or 1;

i = 0 or 1;

- h + i = 1 or 2