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    • 专利摘要:
    The present invention relates to an organopolysiloxane (A) obtainable by reaction, at a temperature between 0 ° C and 150 ° C, between - at least one compound (C) selected from organic compounds comprising at least one alkene function or alkyne 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 or alkyne function 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 (I.1) and (I.2) of the following formulas: The present invention also relates to compositions comprising these organopolysiloxanes (A) and their uses.
    公开号:FR3030536A1
    申请号:FR1463055
    申请日:2014-12-22
    公开日:2016-06-24
    发明作者:Francois Ganachaud；Etienne Fleury；De Almeida Daniel Portinha；Aymeric Genest；Emmanuel Pouget
    申请人:Bluestar Silicones France SAS；
    IPC主号:
    专利说明:

    [0001] 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-fog additive, anti-foam additive, electrical conductor, antistatic additive , antibacterial additive, anti-corrosion, anti-fire or for thin film coating.
    [0002] 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 process 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 0 ° C. and 150 ° C., between at least one compound (C) chosen from the compounds organic compounds comprising at least one alkene or alkyne function of which at least one of the substituents is an acid function and the organic compounds comprising at least one acid function and at least one alkene or alkyne function of which at least one of the substituents is a group electron; and at least one organopolysiloxane (B) selected from organopolysiloxanes comprising siloxyl units (1.1) and (1.2) of the following formulas: YaZibSiO4 (a + b) Zc2SiO4_c 2 (1.1); 2 (1.2) in which: 35 - 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 (1.3): -E- (NH-G) h- (NH2), (1.3) 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 Z1 and Z2, 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 an OR1 radical; with R1 representing a linear, cyclic or branched C1-C15 hydrocarbon radical, and preferably Z1 and Z2 represent a monovalent hydrocarbon group selected from the group consisting of alkyl groups having 1 to 8 carbon atoms, the alkenyl groups having from 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 a radical-OR1 with R1 which represents a C1-C15 hydrocarbon radical, linear, cyclic or branched, and even more preferably selected from the group consisting of a methyl, ethyl, propyl, 3,3,3-trifluoropropyl, vinyl, hydroxyl group 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 (1.3). In the context of the present invention, the term "electron-withdrawing group" is understood to mean a group that 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 bonds depleted in electron. 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 ketone, acid, amide, phosphonate ester, phosphonic acid, sulphonic acid, sulphone, ester, thioester, NO2 group, ON group, etc. In the context of the present application, we mean: by acid function including carboxylic acid functions, sulfonic acids and phosphonic acids. 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 electroattractor. This compound C can then react according to an Aza-Michael reaction with primary or secondary amines as described in the publication "Michael add 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): R 2 R 4 (000R 5 (II) in which: R 2, R 3 and R 4, identical or different, represent a hydrogen atom, a COOH group or a group C1 to 03 alkyl, preferably C1 to 03, preferably methyl, R5 is 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), R2 and R3, which may be identical or different, represent a hydrogen atom or a C1 to C6 alkyl group, preferably a C1 to C3 alkyl group, preferably a methyl group; hydrogen, a C1 to C6 alkyl group, preferably a C1 to C3 alkyl group, preferably a methyl group, or a COOH group; R5 represents a hydrogen atom, an alkyl group or an aryl group, wherein the alkyl group is aryl compounds comprise at least one COOH group, preferably the compounds (C) of the invention are selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, 2-carboxyethylacrylate, 3-carboxypropylacrylate, maleic acid, fumaric acid, 2- (acryloyloxy) acid; 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) -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, acid (1 phenylvinyl) phosphonic acid, 3- (vinylsulfonyl) propanoic acid, 2- (vinylsulfonyl) acetic acid, 2- (vinylsulfonyl) succinic acid, acetylene dicarboxylic acid and propiolic acid.
    [0003] 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.
    [0004] Preferably, the organopolysiloxanes (B) may have a linear, branched, or cyclic structure. When it is a linear organopolysiloxane, these consist essentially of "D" siloxyl units, chosen in particular from the group consisting of the Y2SiO2 / 2, YZ1SiO2 / 2 and Z22S102 / 2 siloxyl units and siloxyl units. M ", especially selected from the group consisting of siloxyl units Y3Si01 / 2, YZ12Si0112, Y2Z1Si0112 and Z23Si0112, Y, Z1 and Z2 being as defined above, it 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 (1.2) of the following formulas: YaZibSiO4 (a + b) Z2SiO c 4 -c 2 (1.1); 2 (1.2) in which: Y and Z1 and Z2 have the definitions given above; - a = 1 or 2, h = 0, 1 or 2 and a + b = 2 or 3 - c = 1 or 2. Particularly preferably, the organopolysiloxanes (B) are chosen from organopolysiloxanes comprising (1.1) selected from the group consisting of YZ1SiO2 / 2 and YZ12SiO112 and units (1.2) selected from the group consisting of Z22Si0212 and Z23Si01,2, the Y, Z1 and Z2 being as defined above, it 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. 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 10.10-2 mol / g, and preferably 5.10-5. and 5.10-2 mol / g.
    [0005] Preferably, the organopolysiloxanes (B) may be chosen from the compounds of formula III (III) with k = 1 to 1000, H2NSho, E-Sho ... 1-, SINH2 preferably 1 to 800 II -Si, I -Si 10-L 1 0 NH 2 (IV) with 1 = 1 to 1000, preferably 1 to 800 and m = 1 to 150, preferably 1 to 100; Si -Si, 1.-Si I 1 -OH NH (V) with n = 1 to 1000, preferably 1 to 800 and o = 1 to 150, preferably 1 to 100; (P) with p = 1 to 1000, preferably 1 to 800. In a particular embodiment, the organopolysiloxane (B) may be in emulsion.
    [0006] 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 CC double bond 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). The ratio r corresponds to the following relation: n (C = C, CC) 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 functions of the organopolysiloxane (B). The ratio J corresponds to the following relationship: I - number of moles of the compound (B) x number of amine functions of the compound (B) Amine function means primary or secondary amines. It must therefore be understood that one mole of primary amine function contains two moles of NH bonds and one mole of secondary amine function contains one mole of NH bonds. Preferably, the ratio J is between 0.01 and 20, preferably between 0.5 and 3. Preferably, the ratio r is between 0.01 and 10, preferably between 0.05 and 2. Preferably the ratio J is between 0.01 and 20, preferably between 0.5 and 3 and the ratio r is between 0.01 and 10, preferably between 0.05 and 2. Preferably, the organopolysiloxane ( B) has a dynamic viscosity measured at 25 ° C with an imposed stress rheometer, including TA-DHRII, between 1 and 100 000 mPa.s, preferably between 100 and 50 000 mPa.s. number of moles of the compound (C) x number of acid functions of the compound (C) Particularly advantageously, by the process used, the organopolysiloxane (A) has a dynamic viscosity measured at 25.degree. an imposed stress rheometer, especially TA-DHRII, at least 10 times higher than that of the organopolysiloxane (B).
    [0007] 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.
    [0008] The present invention also relates to a process for the preparation of an organopolysiloxane (A) comprising bringing into contact, at a temperature of between 0 and 150 ° C., 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 or alkyne function 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 (1.2) of the following formulas: YaZibSiO4 (a + b) Zc2SiO4_c 2 (1.1); 2 (1.2) 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 (1.3): (1.3) 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 Z1 and Z2, 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 an OR1 radical; with R1 which represents a linear, cyclic or branched C1-Clo hydrocarbon radical, and preferably Z1 and Z2 represent a monovalent hydrocarbon group selected from the group consisting of alkyl groups having from 1 to 8 carbon atoms, the alkenyl groups having from 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 a radical-OR1 with R1 which represents a linear C1-C10 hydrocarbon radical, cyclic or branched, and even more preferably selected from the group consisting of 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 (1.3). 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 between the amine functions of the organopolysiloxane (B) and said acid functional groups of the compound (C). Particularly advantageously, the combination of these two reactions makes it possible to obtain an organopolysiloxane (A) whose viscosity, measured at 25 ° C., with an imposed stress rheorometer, in particular TA-DHRII, at least 10 times greater than that organopolysiloxane (B). According to the different 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.
    [0009] 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.
    [0010] The compound (C) and the organopolysiloxanes (B) and (A) are as defined above. Preferably, the process of the present invention is carried out at a temperature between 10 and 100 ° C, preferably between 15 and 70 ° C.
    [0011] The process can be carried out in the presence of microwave and / or ultrasonic irradiation. Particularly advantageously, the process of the present invention can be carried out in bulk or in the presence of a solvent. The solvent is especially chosen from: polar protic 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).
    [0012] 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.
    [0013] 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 μm (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 of between 0.001 and 300 μm (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 quantity of filler of between 1% and 50% by weight, preferably between 1% and 30% by weight, with respect 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).
    [0014] 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. 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.
    [0015] 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 the ratio r, as defined above, above, is between 0.01 and 10, preferably between 0.05 and 2. 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; pigments, additives for thermal resistance, resistance to oils or fire resistance, for example metal oxides.
    [0016] 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.
    [0017] 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). Organopolysiloxanes (A) can also be used as additives and especially as adhesion promoters, anti-fog, antifoam, anti-static, anti-bacterial, anti-corrosion, anti-fire, anti-graffiti or for anti-fogging agents. 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, antifoam compositions, etc. The present invention also relates to a composition X for the preparation of an organopolysiloxane (A) according to the invention, comprising: at least one compound (C) chosen from organic compounds comprising at least one alkene or alkyne function of which at least one one of the substituents is an acid function and the organic compounds comprising at least one acid function and at least one alkene or alkyne function of which at least one of the substituents is an electron-withdrawing group; and at least one organopolysiloxane (B) comprising siloxyl units (1.1) and (1.2) of the following formulas: YaZibSiO4 (a + b) Zc2SiO4_c 2 (1.1); 2 (1.2) in which: - a = 1 or 2, h = 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 (1.3): (1.3) 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 Z1 and Z2, 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 an OR1 radical; with R 1 which represents a linear, cyclic or branched C 1 -C 10 hydrocarbon radical, and preferably Z 1 and Z 2 represent a monovalent hydrocarbon group selected from the group consisting of alkyl groups having from 1 to 8 carbon atoms, the alkenyl groups having from 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 C 1 -C 10 hydrocarbon radical, cyclic or branched, and even more preferably selected from the group consisting of 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 (1.3). The compound (C) and the organopolysiloxanes (A) and (B) being as defined above.
    [0018] The present invention will now be described by way of non-limiting examples.
    [0019] Examples In the examples below, given by way of illustration, reference is made to the following definitions: Mn represents the number-average molar mass. PDMS = polydimethylsiloxane The PDMSs used in the examples which follow correspond to one of the following formulas: ## STR1 ## ## STR1 ## ## STR2 ## Organosiloxane (2): Commercial, Gelest SIAO604.5 3-aminopropylmethylbis (trimethylsiloxy) silane, III-Si-O-Si-O-Si-II (IV) ( V) NH2-PDMS (3): Gelest, Mn-3000g / 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) amount of N-H bond per gram = 8.0 x 10-5 mol / g; Mn-50000g / mol - PDMS (5): Gelest; compound of formula (III) Mn-30000g / mol; amount of N-H bond per gram = 1.33.10-4 mol / g - PDMS (6): Gelest; compound of formula (IV) N-H bond amount per gram = 1.71.10-3 mol / g; - PDMS (7): Gelest; compound of formula (IV); amount of N-H bond per gram = 2.43 × 10 -3 mol / g; - PDMS (8): Gelest; compound of formula (IV); amount of N-H bond per gram = 5.14 × 10 -3 mol / g; - PDMS (9): Gelest; compound of formula (V) amount of N-H bond per gram = 6.54 × 10 -3 mol / g; PDMS (10): Gelest; Compound of formula (V); amount of N-H bond per gram = 8.57 × 10 -4 mol / g; - PDMS (11): Bluestar Silicones; compound of formula (V) amount of N-H bond per gram = 3.21 × 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 40 mm in diameter and having a truncation of 52 μm. The viscosity was recorded as a function of the shear rate (0.01 -100 s-1) at 25 ° C..35 NMR: The 1H nuclear magnetic resonance (NMR) spectra were recorded on a 400 Bruker Avance III spectrometer. MHz. The samples were dissolved either in deuterated chloroform or in a CDCl3 / MeOH mixture (60/40 mol) and analyzed at 27 ° C.
    [0020] Rheology The rheological analyzes were carried out using an imposed stress rheometer (TA-DHRII) at 25 ° C using a plane / plane geometry (40 mm diameter). Frequency scans were recorded in the linear viscoelastic domain of the products between 100 and 0.01 Hz. EXAMPLE 1 Preparation of ORGANOSILOXANE (1) ORGANOSILOXANE (1) was prepared according to the following protocol: (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (5.0 g) and hexamethyldisiloxane (20.1 g) were mixed in a two-neck flask surmounted by a condenser in the presence of tetramethylammonium hydroxide dissolved in methanol (0.5 g). boy Wut). 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-necked flask, 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. 1 H NMR analysis of the reaction medium taken at 1, 4, 6, 8 and 24 h of reaction, made it possible to show a disappearance of the 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 2 bis test was also carried out following Example 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 in Example 2 is not due to a polymerization reaction of acrylic acid but to the reaction of Aza-Michael between the NH bonds carried by ORGANOSILOXANE (1) and the carbon-carbon double bond of acrylic acid.
    [0021] EXAMPLE 3 Reaction of Organosiloxane (2) with Acrylic Acid, Propionic Acid or Butyl Acrylate In a sealed container, the organosiloxane (2) and acrylic acid (AA) were mixed. (r = 0.5, J = 1) or propionic acid (AP) (r = 0, J = 1) or butyl acrylate (BuA) (r = 0.5, J = 0). An exothermic reaction is observed when adding acrylic acid or propionic acid. The maximum temperature reached is 92 ° C and 87 ° C respectively. After 10 minutes, the temperature of the reaction mixture is again equal to room temperature (25 ° C.). The dynamic viscosity of the products obtained after 168 hours was measured at different shear rates (0.1-100 s-1).
    [0022] The results obtained are summarized in Table 1. TEST Products Dynamic viscosity (mPa. $) 1 ORGANOSILOXANE (2) 3.1 ± 0.6 2 ORGANOSILOXANE (2) / BuA 6.9 ± 0.4 3 ORGANOSILOXANE (2) / AP 580 ± 5 4 ORGANOSILOXANE (2) / AA 5900 ± 50 Table 1 No increase in temperature is noted during the mixing of butyl acrylate with ORGANOSILOXANE (2) thus revealing a lack of acid-base reaction (butyl acrylate does not include acid functions). It is noted a small increase in the dynamic viscosity of the product obtained by reaction of butyl acrylate with ORGANOSILOXANE (2) with respect to the initial dynamic viscosity of ORGANOSILOXANE (2). Without wishing to be bound by any theory, this increase in dynamic viscosity is due to the Aza-Michael reaction between the NH bonds carried by ORGANOSILOXANE (2) and the carbon-carbon double bond of butyl acrylate. An increase in the dynamic viscosity of the products obtained by reaction of propionic acid with ORGANOSILOXANE (2) and by partial reaction (conversion 40% at t = 168 h) of acrylic acid with ORGANOSILOXANE (2), is noted relative to the initial viscosity of ORGANOSILOXANE (2). 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 ORGANOSILOXANE (2) and the acid functions of propionic acid and acrylic acid. It is noted a very strong increase in the dynamic viscosity of the product obtained by partial reaction (conversion 40% on the basis of the 1 H NMR, at t = 168 h, acrylic functions due to the reaction of Aza-Michael between the bonds NH borne by ORGANOSILOXANE (2) and acrylic acid) of acrylic acid with ORGANOSILOXANE (2) relative to the product obtained by reaction of propionic acid with ORGANOSILOXANE (2). These results show that the Aza-Michael reaction associated with an acid-base reaction leads to a product which has a higher dynamic viscosity compared to the starting ORGANOSILOXANE (2). Example 4: Influence of Temperature on Acrylic Acid Use The reaction of Example 2 was repeated at different temperatures: 25 ° C (Run 5), 50 ° C (Run 6) and 70 ° C (Run 7). The conversion of acrylic fluxes over time was followed by 1H NMR. The results are shown in Table 2 below: No. TEST 5 6 7 Time (h) Conversion (° / 0) 0 0 0 0 1 16 39 84 2 18 54/4 23 71 98 6 27 81/7 / / 100 These results show that an increase in temperature makes it possible to obtain a total conversion of acrylic functions as early as 7h at 70.degree.
    [0023] 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 5: Reaction of PDMS (3) with Acrylic Acid by Mass In a 15mL monocolumn flask, 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-reactive 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 1H NMR at 96% at t = 72h. 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 shown in Table 3 below. No. TEST Products Dynamic Viscosity (mPa. $) 8 PDMS (3) 57.5 ± 6.5 9 PDMS (3) / AA t = 0 1225 ± 50 9 PDMS (3) / AA t = 72h 1.75.105 ± 5.103 Table 3 These results show that 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 Example 6: Variation in the nature of PDMS, J and r PDMS 4 to 11 and acrylic acid were reacted, by mass, in a suitable plastic container. The reaction mixture was homogenized using a high speed planetary mixer (2750 rpm) for 2 minutes and 30 seconds.
    [0024] 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 according to the various PDMSs are summarized in Table 4 below: No. PDMS TEST PDMS (4) 0.52 11 PDMS (5) 0.54 12 PDMS (6) 0.50 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 (11) 0 Table 4 The products obtained were analyzed by 1H NMR after 17 days of reaction at room 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 5 below: No. TEST Conversion Solubility (10g / L) (%) CDCl3 H20 IPA THF MCH 10 67 S - - - - 11 68 S - - - - 12 72 S - - - - 13 70 S - - - - 14 - IDD - - 15 - IIIII 16 87 SI - SS 17 84 SI - SS 18 90 SI - SS Table 5 Legend: S: soluble; I: insoluble; D: dispersible; -: not tested CDCI3: Deuterated chloroform; H2O: water; IPA: Isopropanol; THF: Tetrahydrofuran; MCH: Methylcyclohexane The products obtained all have a viscosity at least 10 times greater than the respective starting PDMS. The products obtained can be called viscoelastic liquids.
    [0025] 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 was recorded under the following conditions: Deformation (8) of 0.1% applied for the test 16 and the PDMS ( 10), deformation (8) of 0.03% applied for the test 17 and deformation (8) of 0.2% applied for the test 18 and the PDMS (11) .The results obtained after 18 days of The reaction is grouped in the following two tables 6 and 7: No. PDMS TEST (10) 16 17 Frequency (Hz) G '(Pa) G "(Pa) G' (Pa) G" (Pa) G '(Pa) G "(Pa) 100 3.6.102 1.7.102 2.2.105 3.9.104 2.6.105 4.9.104 10 7 45 1.7.105 4.8.104 1.9.105 4.2.104 1 1.3 5 8.3.104 5.3.104 1.2.105 5.3.104 0.1 1.1 0.5 1.9.104 2.6.104 3.9.104 4.2.104 0.01 / / 1.3.103 5.7.103 4.8.103 1.1.104 Crossing G '/ G " Crossing G '/ G "Crossing G' / G" Frequency (Hz)> 100 0.2 0.1 Table 6 No. TEST PDMS (11) 18 Frequency G, (Fa) G- (Fa) G '(Fa) G "(Pa) (Hz) 100 2.1.103 4.2.103 1.2.105 1.8.104 10 1.4.102 6.5.102 9.6.104 2.6.104 1 4 76 4.9.104 2.8.104 0.1 0.2 8 1.7.104 1.5.104 0.01 0.2 0.9 3.4.103 5.3.103 Crossing G '/ G "Crossing G' / G" Frequency> 100 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 18. The three products obtained are therefore viscoelastic liquids at t = 18 days.
    [0026] 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 with respect to PDMS (11), this increase being due to the reaction of Aza- Michael coupled with the acid-base reaction.
    [0027] From these results the following complex viscosities could be deduced: No. TEST PDMS (10) 16 17 Frequency (Hz) n * (Pa. $) 100 0.6 3.5.102 4.2.102 10 0.7 2.8.103 3.1.103 1 0.8 1.6.104 2.2.104 0.1 1.9 5.2.104 9.1.104 0.01 / 9.3.104 2.0.105 Table 815 No. TEST PDMS (11) 18 Frequency ( Hz) n * (Pas) 100 7 2.0.102 10 11 1.6.103 1 12 9.0.103 0.1 13 3.6.104 0.01 15 1.0.105 Table 9 The results show a decrease in complex viscosity when the frequency increases. By letting the products evolve towards 100% conversion, they evolve towards viscoelastic solids. EXAMPLE 7 Reaction of PDMS (3) with Acrylic Acid in the Presence of a Solvent (25 ° C.) In a 25 mL single-neck 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. 1H NMR analysis of the product obtained in the CDCI3 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 1H NMR at 37%.
    [0028] Example 8: 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: tert-butanol, IPA / water solution (50/50 mol) or saturated solution of ammonia (1 g) and the mixture is stirred magnetically at 50 ° C for 24 hours. The conversion of the acrylic functions is followed by 1H NMR and the results are shown in Table 10 below. No. TEST Reaction medium Conversion (° / 0) as a function of time (h) Oh 1h 4h 8h 24h 9 By mass 0 8 17 31 69 19 Tert-Butanol 0 5 12 25 64 20 IPA / Water 0 0 3 5 35 21 Ammonia solution 0 8 18/56 Table 10 These data show, in combination with the results of Examples 2, 5 and 7, that the process of the invention can be carried out in the presence of different solvents or in bulk and that a functionalized organopolysiloxane can be obtained under these various conditions. EXAMPLE 9 Reaction of Organosiloxane (2) with 2-Carboxyethylacrylate In a sealed pillbox, the organosiloxane (2) and 2-carboxyethlacrylate were mixed in proportions such that r = 0.5 and J = 1. The mixture is stirred magnetically for 48 h at 50 ° C at atmospheric pressure. An 1 H NMR analysis of the reaction medium taken at 1, 4, 7, 24 and 48 h of reaction, made it possible to show a disappearance of the 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.
    [0029] At t = 48h, a conversion of the acrylate functions of a value of 96% is reached. Table 11 below groups the data in terms of conversion versus reaction time. Time (h) Conversion (° / 0) 1 62.0 4 73.2 6.5 77.1 24 90.1 48 96.4 Table 1120
    权利要求:
    Claims (18)
    [0001]
    REVENDICATIONS1. Organopolysiloxane (A) obtainable by reaction, at a temperature between 0 ° C and 150 ° C, between at least ucts.genposé (C) selected from organic compounds comprising at least one alkene or alkyne function of which at least one of the substituents is an acid function and the organic compounds comprising at least one acid function and at least one alkene or alkyne function of which at least one of the substituents is an electron-withdrawing group; and at least one organopolysiloxane (B) selected from organopolysiloxanes comprising siloxyl units (1.1) and (1.2) of the following formulas: VlbSiO44 & O,) ZSiO 2 (1.1); 2 (1.2) in which: 15 - a = 1 or 2, h = 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 (1.3): -E- (NH-G) h- (NH2); (1.3) wherein: - h = 0 yes; - i = 0 yes; - 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 Z1 and Z2, 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-radical; OR1 with R1 which represents a linear, cyclic or branched C1-C10 hydrocarbon radical, and preferably Z1 and Z2 represent a monovalent hydrocarbon group selected from the group consisting of alkyl groups having from 1 to 8 carbon atoms, the groups alkenyls 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-OR1 with R1 which represents a linear C1-C10 hydrocarbon radical , cyclic or branched, and even more preferably selected from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, vinyl, hydroxyl yl, 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 (1.3).
    [0002]
    Organopolysiloxane (A) according to claim 1, wherein the compound (C) is selected from organic compounds comprising at least one carbon-carbon double bond and at least one carboxylic acid function.
    [0003]
    Organopolysiloxane (A) according to claim 1 or 2, in which the compound (C) is chosen from compounds of the formula (II) wherein R 2, R 3 and R 4, which may be identical or different, , represent a hydrogen atom, a COOH group, or a C1 to C6, preferably C1 to C3, alkyl group, preferably methyl; R5 represents a hydrogen atom, an alkyl group or an aryl group, wherein the alkyl and aryl comprise at least one COOH group.
    [0004]
    4. Organopolysiloxane (A) according to one of claims 1 to 3, 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, 2- (acryloyloxy) -2-phenylacetic acid, 4- (acryloyloxy) butanoic acid, 2- (acryloyloxy) -2-methylpropanoic acid, the acid
    [0005]
    5- (acryloyloxy) pentanoic acid, (E) -but-2-enoic acid, (Z) -prop-1-ene-1,2,3-tricarboxylic acid, cinnamic acid, sorbic acid , 2-hexenoic acid, 230 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. 15. Organopolysiloxane (A) according to one of claims 1 to 4, in which the organopolysiloxane (B) is chosen from organopolysiloxanes comprising siloxyl units (1.1) and (1.2) of the following formulas: VlbSiOhx ') Zc2SiO4_c 2 (1.1) -2- (1.2) in which: Y and Z1 and Z2 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.
    [0006]
    6. Organopolysiloxane (A) according to one of claims 1 to 5, characterized in that the organopolysiloxane (B) has a degree of polymerization of between 2 and 5000, preferably between 2 and 500.
    [0007]
    Organopolysiloxane (A) according to one of claims 1 to 6, 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.
    [0008]
    8. Organopolysiloxane (A) according to any one of claims 1 to 7, 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).
    [0009]
    9. A process for the preparation of an organopolysiloxane (A) comprising bringing into contact, at a temperature of between 0 and 150 ° C., at least one compound (C) chosen from organic compounds comprising at least one alkene or alkyne function. at least one of the substituents is an acid function and the organic compounds comprising at least one acid function and at least one alkene or alkyne function of which at least one of the substituents is an electron-withdrawing group; and at least one organopolysiloxane (B) selected from organopolysiloxanes comprising siloxyl units (1.1) and (1.2) of the following formulas: YaZ1bSiO4 <a + b) Z2SiO c4-c 2 (1.1) 2 (L2) 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 ( 1.3): -E- (NH-G) h- (NH 2); (1.3) in which: - h = 0 or 1; - i = 0 yes; - 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 Z1 and Z2, 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-radical; OR1 with R1 which represents a linear, cyclic or branched C1-C10 hydrocarbon radical, and preferably and Z2 represents a monovalent hydrocarbon group selected from the group consisting of alkyl groups having from 1 to 8 carbon atoms, the 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-OR1 with R1 which represents a linear C1-C10 hydrocarbon radical cyclic or branched, and even more preferably selected from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, vinyl, hydrous oxyl, ethoxyl, methoxyl, xylyl, tolyl and phenyl; said polyorganosiloxane O3) comprising, per molecule, at least one siloxyl unit (1.1) bearing at least one functional group of formula (1.3).
    [0010]
    10. Process according to claim 9, carried out at a temperature of between 10 and 100 ° C, preferably between 15 and 70 ° C.
    [0011]
    11. Process according to any one of claims 9 or 10, carried out in bulk or in the presence of a solvent, in particular chosen from protic polar polar polar aprotic and apolar solvents. 35
    [0012]
    12. Process according to any one of claims 9 to 11, 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).
    [0013]
    The process according to any one of claims 9 to 12, 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 borne by the organopolysiloxane (B) n (C = C or CC) r = n (N-H) is between 0.01 and 10, preferably between 0, 05 and 2.
    [0014]
    The process according to any one of claims 9 to 13, 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) j = number of moles of the compound (B) x number of amine functions of the compound (B) is between 0.01 and 20, preferably between 0.5 and 3.
    [0015]
    15. Composition K1 comprising at least one organopolysiloxane (A) according to one of claims 1 to 8, 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, additive additives for increasing 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, 5, 6 or 7.
    [0016]
    16. Use of at least one organopolysiloxane (A) according to one of claims 1 to 8, or a composition K1 according to claim 15, in the woundcare, for example coating of dressings, manufacture of external prostheses, anti cushions -scars; 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 adhesion promoter additives, anti-fog, anti-foam, antistatic, antibacterial, anti-corrosion, anti-fire, anti graffiti; for temporary printing, or for thin film coating.
    [0017]
    17. Use of at least one organopolysiloxane (A) according to one of claims 1 to 8, or a composition K1 according to the claim in paints, coatings, adhesives, mastics, personal care, health care, textile processing, electronics, automobiles, rubbers, anti-foam compositions.
    [0018]
    18. Composition X for the preparation of an organopolysiloxane (A) according to one of Claims 1 to 8, comprising: at least one compound (C) chosen from organic compounds comprising at least one alkene or alkyne function of which at least one one of the substituents is an acid function and the organic compounds comprise at least one acid function and at least one alkene or alkyne function 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 (1.2) of the following formulas: embedded image 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 may be identical or different, represent a functional group of formula (1.3): -E- (NH-G) ) h- (1 ^ 11-12), (1.3) in which: - h = 0 yes; 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 Z1 and Z2, 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-OR1 with R1 which represents a linear, cyclic or branched C1-C10 hydrocarbon radical and preferably Z1 and Z2 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. carbon atoms optionally comprising one or more fluorine atoms, a hydroxyl group, or a radical-OR1 with R1 which represents a linear, cyclic C1-C10 hydrocarbon radical or branched, and even more preferably selected from the group consisting of 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 (1.3). 15
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    同族专利:
    公开号 | 公开日
    JP2020023703A|2020-02-13|
    FR3030536B1|2018-06-15|
    KR20170134315A|2017-12-06|
    EP3237070A1|2017-11-01|
    US20180265668A1|2018-09-20|
    WO2016102498A1|2016-06-30|
    CN107429063A|2017-12-01|
    US10358541B2|2019-07-23|
    CN107429063B|2021-03-23|
    JP2018501393A|2018-01-18|
    KR20190093710A|2019-08-09|
    KR102098731B1|2020-04-08|
    JP6673934B2|2020-03-25|
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    法律状态:
    2015-11-10| PLFP| Fee payment|Year of fee payment: 2 |
    2016-06-24| PLSC| Publication of the preliminary search report|Effective date: 20160624 |
    2016-11-11| PLFP| Fee payment|Year of fee payment: 3 |
    2017-11-13| PLFP| Fee payment|Year of fee payment: 4 |
    2018-08-10| CD| Change of name or company name|Owner name: ELKEM SILICONES FRANCE SAS, FR Effective date: 20180709 Owner name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE, FR Effective date: 20180709 Owner name: UNIVERSITE JEAN MONNET SAINT ETIENNE, FR Effective date: 20180709 Owner name: INSTITUT NATIONAL DES SCIENCES APPLIQUEES LYON, FR Effective date: 20180709 Owner name: UNIVERSITE CLAUDE BERNARD LYON 1, FR Effective date: 20180709 |
    2019-11-15| PLFP| Fee payment|Year of fee payment: 6 |
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    2021-11-15| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1463055|2014-12-22|
    FR1463055A|FR3030536B1|2014-12-22|2014-12-22|ORGANOPOLYSILOXANES AND PROCESS FOR THEIR PREPARATION|FR1463055A| FR3030536B1|2014-12-22|2014-12-22|ORGANOPOLYSILOXANES AND PROCESS FOR THEIR PREPARATION|
    US15/537,132| US10358541B2|2014-12-22|2015-12-21|Organopolysiloxanes and methods for preparing same|
    JP2017551023A| JP6673934B2|2014-12-22|2015-12-21|Organic polysiloxane and method for producing the same|
    PCT/EP2015/080843| WO2016102498A1|2014-12-22|2015-12-21|Organopolysiloxanes and methods for preparing same|
    CN201580074101.6A| CN107429063B|2014-12-22|2015-12-21|Organopolysiloxane and method for producing the same|
    KR1020177017210A| KR20170134315A|2014-12-22|2015-12-21|Organopolysiloxanes and methods for preparing same|
    EP15820515.3A| EP3237070A1|2014-12-22|2015-12-21|Organopolysiloxanes and methods for preparing same|
    KR1020197022903A| KR102098731B1|2014-12-22|2015-12-21|Organopolysiloxanes and methods for preparing same|
    JP2019175456A| JP2020023703A|2014-12-22|2019-09-26|Organopolysiloxane and production method of the same|
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