Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
  • A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q15/00—Anti-perspirants or body deodorants
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
  • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
  • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G85/00—General processes for preparing compounds provided for in this subclass
  • C08G85/002—Post-polymerisation treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G85/00—General processes for preparing compounds provided for in this subclass
  • C08G85/004—Modification of polymers by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/10—General cosmetic use
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/70—Post-treatment
  • C08G2261/72—Derivatisation
  • C08G2261/728—Acylation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups

Definitions

• 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.
• organopolysiloxane A
• 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.
• organopolysiloxane compounds having modulable viscoelastic properties in order to adapt to any type of use.
• 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;
• organopolysiloxane (B) chosen from organopolysiloxanes comprising siloxyl units (1.1) and (I.2) of the following formulas:
• 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;
• 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
• polyorganosiloxane (B) comprising, per molecule, at least one siloxyl unit (1.1) bearing at least one functional group of formula (I.3).
• the organopolysiloxane (A) as described above is obtained at a reaction temperature of between 10 and 70 ° C., preferably between 15 and 70 ° C.
• 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.
• the electron-withdrawing group depletes the alkene or alkyne functions in electrons.
• the term "acid function" is understood to mean in particular the carboxylic acid, sulphonic acid and phosphonic acid functions.
• 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.
• 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.
• 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.
• 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.
• 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
• 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.
• the compound (C) is acrylic acid or 2-carboxyethylacrylate.
• the compound (C) is acrylic acid.
• the organopolysiloxanes (B) may have a linear, branched, or cyclic structure.
• 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.
• organopolysiloxanes (B) are chosen from organopolysiloxanes comprising siloxyl units (1.1) and (I.2) of the following formulas:
• Y and Z 1 and Z 2 have the definitions given above;
• 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.
• the organopolysiloxanes (B) have a degree of polymerization of between 2 and 5000, preferably between 2 and 1500, more preferably between 2 and 500.
• the organopolysiloxanes (B) comprise a number of siloxyl units (1.1) of between 1 and 100, preferably between 2 and 80.
• 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.
• organopolysiloxanes (B) may be chosen from compounds of formula:
• 1 to 150 preferably 1 to 100;
• 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.
• the organopolysiloxane (B) may be in emulsion. All of the preferred characteristics defining the organopolysiloxanes (B) can be combined with one another.
• 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)
• 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.
• 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.
• 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.
• 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.
• 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. .
• 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.
• 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:
• 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;
• Z 1 and Z 2 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, hydroxy
• polyorganosiloxane (B) comprising, per molecule, at least one siloxyl unit (1.1) bearing at least one functional group of formula (I.3).
• 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.
• 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.
• 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).
• the organopolysiloxane (A) obtained can be a viscoelastic liquid or a viscoelastic solid.
• 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.
• the organopolysiloxane (B) can be prepared in situ in the presence of the compound (C).
• the process of the present invention is carried out at a temperature between 10 and 70 ° C, preferably between 15 and 70 ° C.
• 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.
• 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).
• 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.
• 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 ⁇ (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.
• non-siliceous fillers examples include 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 ⁇ (micrometers) and a BET surface area of less than 100 m 2 / g.
• 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).
• 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).
• 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.
• 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.
• the ratio J is between 0.01 and 20, preferably between 0.5 and 3, even more preferentially between 0.5 and 1.
• 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.
• the composition K1 may be an organopolysiloxane composition.
• the composition K1 may further comprise at least one filler and / or at least one organopolysiloxane.
• composition K1 may also comprise one or more usual functional additives.
• families of usual functional additives mention may be made of:
• additives for heat resistance, resistance to oils or fire resistance for example metal oxides.
• composition K1 may also comprise an organopolysiloxane comprising at least one carboxylic function.
• composition K1 may also comprise at least one organopolysiloxane (B) as defined above.
• the organopolysiloxane (A) has a higher dynamic viscosity than the starting organopolysiloxane (B).
• 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.
• 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:
• 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;
• At least one organopolysiloxane (B) comprising siloxyl units (1.1) and (I.2) of the following formulas:
• 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;
• 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,
• polyorganosiloxane (B) comprising, per molecule, at least one siloxyl unit (1.1) bearing at least one functional group of formula (I.3).
• the compound (C) and the organopolysiloxanes (A) and (B) being as defined above.
• Mn represents the average molar mass in number.
• 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 ⁇ . Viscosity was recorded as a function of shear rate (0.01-100 s -1 ) at 25 ° C.
• ORGANOSILOXANE (1) was prepared according to the following protocol:
• ORGANOSILOXANE (1) and acrylic acid are mixed.
• the mixture is stirred magnetically for 24 h at 50 ° C at atmospheric pressure.
• 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.
• 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).
• 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
• results 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.
• Example 6 Reaction of PDMS (3) with Acrylic Acid in the Presence of a Solvent (25 ° C.)
• PDMS (3), isopropanol (IPA, 33%) are mixed by weight relative to the total weight of PDMS (3) and acrylic acid) and acrylic acid.
• IPA isopropanol
• 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.
• Example 7 Influence of the solvent (50 ° C.)
• 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
• 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.
• the product obtained is colorless, transparent, homogeneous and soluble in THF and methylcyclohexane.
• the product obtained is slightly yellowish and is not soluble in THF or in methylcyclohexane.
• 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.
• 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 .
• 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.
• a hydrophobic fumed silica (Aerosil® R104)
• 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%.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Public Health (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Veterinary Medicine (AREA)
• Dermatology (AREA)
• Epidemiology (AREA)
• Birds (AREA)
• Silicon Polymers (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=52692850

Family Applications (1)

Country Status (7)

Families Citing this family (12)

Family Cites Families (10)

• 2014
  • 2014-12-22 FR FR1463055A patent/FR3030536B1/fr active Active
• 2015
  • 2015-12-21 KR KR1020197022903A patent/KR102098731B1/ko active IP Right Grant
  • 2015-12-21 CN CN201580074101.6A patent/CN107429063B/zh active Active
  • 2015-12-21 JP JP2017551023A patent/JP6673934B2/ja active Active
  • 2015-12-21 US US15/537,132 patent/US10358541B2/en active Active
  • 2015-12-21 WO PCT/EP2015/080843 patent/WO2016102498A1/fr active Application Filing
  • 2015-12-21 EP EP15820515.3A patent/EP3237070A1/fr active Pending
  • 2015-12-21 KR KR1020177017210A patent/KR20170134315A/ko not_active IP Right Cessation
• 2019
  • 2019-09-26 JP JP2019175456A patent/JP2020023703A/ja active Pending

Also Published As

Similar Documents

Legal Events