EP3759186A1 - Silikonmaterialien - Google Patents

Silikonmaterialien

Info

Publication number
EP3759186A1
EP3759186A1 EP19706704.4A EP19706704A EP3759186A1 EP 3759186 A1 EP3759186 A1 EP 3759186A1 EP 19706704 A EP19706704 A EP 19706704A EP 3759186 A1 EP3759186 A1 EP 3759186A1
Authority
EP
European Patent Office
Prior art keywords
acid
material according
carbon atoms
organopolysiloxane
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19706704.4A
Other languages
English (en)
French (fr)
Inventor
François GANACHAUD
Daniel PORTINHA DE ALMEIDA
Etienne Fleury
Gabriel Duaux
Aymeric GENEST
Emmanuel POUGET
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
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
Original 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 (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 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 filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP3759186A1 publication Critical patent/EP3759186A1/de
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/307—Handling of material to be used in additive manufacturing
    • B29C64/314—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • 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
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy 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
    • C08G77/22—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 silicone materials, their method of preparation and their uses.
  • a first route consists in using a polyorganosiloxane comprising amino groups with an unsaturated acid compound (WO2016102498).
  • the material obtained has good elastic properties but a low tensile strength.
  • a second route (Feng et al., Journal of Polymer Science, part A: polymer chemistry 2017, 55, 903-91 1) consists in bringing into contact a polyorganosiloxane carrying amino groups with a multifunctional acid.
  • the material obtained is hard but brittle and has neither elastic properties nor mechanical properties.
  • An object of the present invention is therefore to provide a silicone material having good elastic and mechanical properties.
  • Another object of the present invention is to provide such a material having healing properties.
  • Yet another object of the present invention is to provide such a material which can be recycled by simple and inexpensive methods.
  • Another object of the invention is also to provide a process for preparing such a material.
  • 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 represents 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 or a hydroxyl group, preferably Z 1 represents 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, and still more preferably Z 1 is selected from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, vinyl, xylyl, tolyl and phenyl;
  • Z 2 represents a monovalent hydrocarbon radical having 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 hydrocarbon radical -C linear 10 or branched, and preferably Z 2 is 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 carbon and aryl groups having 6 to 12 carbon atoms optionally comprising one or more fluorine atoms, or a radical -OR 1 with R 1 which represents a linear or branched C1-C10 hydrocarbon radical, and even more preferably Z 2 is selected from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, vinyl, ethoxyl, methoxyl, xylyl, tolyl and phenyl;
  • organopolysiloxane A comprising, per molecule:
  • At least two terminal units M chosen from the group consisting of the siloxyl units Y 3 SiO 1/2 , YZ 1 2 Si 0 1/2 , Y 2 Z 1 Si 0 1/2 and Z 2 3 Si 0 1/2 and
  • At least one organic compound B bearing at least two carboxylic acid groups and not comprising any unsaturation bearing at least two carboxylic acid groups and not comprising any unsaturation.
  • the reaction is carried out at a temperature between 30 and 200 ° C, preferably between 50 and 150 ° C, preferably between 40 and 100 ° C, more preferably between 50 and 70 ° C.
  • the duration of the reaction at temperature depends on the nature of the reagents and the temperature. Those skilled in the art will be able to adjust the conditions of temperature and heating time to obtain materials having good mechanical and self-healing properties. As an indication, the reaction time at temperature can vary between a few hours at 100 ° C and a few days at 70 ° C.
  • the term "unsaturation in a compound” means a double or triple bond between two carbon atoms.
  • Such compounds are also called saturated compounds.
  • compound B is a saturated organic compound comprising at least two carboxylic acid functions.
  • the silicone material is a supramolecular silicone material and is advantageously in the form of a supramolecular ion network.
  • the reaction between the amine functions of organopolysiloxane A and the carboxylic acid functions of compound B is an acid-base reaction involving ionic interactions.
  • This supramolecular silicone material or supramolecular ionic network may for example be an elastomer.
  • the molar mass is an average molar mass (Mn). The Mn value can be determined by 29 Si NMR or by steric exclusion analysis.
  • the organopolysiloxanes A may have a linear or branched structure with M, D, T Q units used in the silicone nomenclature and corresponding to:
  • R groups identical or different, are monovalent hydrocarbon groups having from 1 to 30 carbon atoms.
  • these essentially consist of D siloxyl units, especially chosen from the group consisting of the siloxyl units Y 2 SiO 2/2 , YZ 1 SiO 2/2 and Z 2 2 SiO 2/2 and terminal siloxy M units, especially selected from the group consisting of Y 3 SiOi / 2 siloxyl units, YZ 1 2 SiOi / 2 , Y 2 Z 1 SiOi / 2 and Z 2 3 SiOi / 2 , Y Z 1 and Z 2 being as defined above.
  • the organopolysiloxanes A are chosen from linear 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 A are chosen from linear organopolysiloxanes comprising units (1.1) chosen from the group consisting of YZ 1 SiO 2/2 and YZ 1 2 SiO 1/2 and units (I.2) chosen from the group consisting of Z 2 2 Si0 2/2 and Z 2 3 Si0 1/2 , the Y, Z 1 and Z 2 being as defined above.
  • the organopolysiloxanes A comprise, per molecule, at least one siloxyl unit (1.1) bearing at least one functional group of formula (I.3) and two units (I.2) for which one and only one of the Z 2 represents a radical -OR 1
  • the organopolysiloxanes A comprise per molecule at least one siloxyl unit (1.1) bearing at least one functional group of formula (I.3) and two units (I.2) for each of which one and only one of Z 2 represents a radical -OR 1 .
  • the organopolysiloxane A comprises two terminal units M of formula Z 2 3 Si0 1/2 in each of which one, and only one, of Z 2 represents a radical -OR 1 .
  • the organopolysiloxanes A of the invention comprise at least two units (1.1) each carrying at least one group (I.3), preferably each carrying a single unit (I.3).
  • the organopolysiloxanes A of the invention comprise:
  • the organopolysiloxanes A of the invention comprise:
  • the organopolysiloxanes A of the invention comprise:
  • the organopolysiloxanes A according to the invention comprise only two radicals -OR 1 which are preferably borne by terminal units M.
  • the organopolysiloxanes A comprise a number of siloxyl units (1.1) of between 1 and 60, preferably between 1 and 20, preferably between 1 and 10.
  • the organopolysiloxanes A comprise a number of siloxyl units (I.2) of between 50 and 950, preferably between 50 and 500, more preferably between 100 and 375.
  • the organopolysiloxanes A comprise a quantity of NH bond expressed in mol per gram of between 1.10 5 and 10.10 2 mol / g, preferably 5 ⁇ 10 5 and 5 ⁇ 10 2 mol / g, more preferably from 1 ⁇ 10 4 to 5 ⁇ 10 3 mol. / g.
  • amine function is meant 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.
  • the compounds A of the invention are in particular chosen from the following compounds:
  • n or p 50 to 950, preferably 50 to 500, preferably 100 to 375 and
  • the compound B may be chosen from the group consisting of the following acids: citric acid, malic acid, acid succinic acid, oxalic acid, malonic acid, succinic acid, tartaric acid, glutaric acid, adipic acid, acid pimelic, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, thapsic acid, phthalic acid, isophthalic acid, terephthalic acid, dipicolinic acid, trimesic acid, isocitric acode, oxalosuccinic acid, tricarballylic acid, homocitric acid, hydroxycitric acid and pamoic acid.
  • compound B is selected from the group consisting of the following acids: citric acid, malic acid and succinic acid. According to a preferred embodiment, compound B is citric acid.
  • ratio J representing the ratio between the number of moles of acid functions of compound B and the number of moles of amine functions of organopolysiloxane A.
  • the ratio J corresponds to the following relationship: number of moles of compound ( 5) x number of acid functions of the compound (B)
  • the ratio J is between 0.5 and 1.5, preferably between 0.8 and 1.2, more preferably between 0.85 and 1.
  • the organopolysiloxane A has a dynamic viscosity measured at 25 ° C. with an imposed stress rheometer, in particular TA-DHRII, of less than 30000 mPa.s, preferably of between 1 and 15000 mPa.s, more preferably between 1 and 10,000 mPa.s and even more preferably between 1 and 8000 mPa.s.
  • the silicone material according to the invention has good mechanical properties while maintaining good hardness, even in the absence of fillers generally used in this type of compounds to enhance the mechanical properties.
  • the supramolecular silicone material according to the invention may have an elongation greater than 100% and a modulus greater than 0.25 MPa.
  • the silicone material according to the invention may comprise fillers, especially reinforcing or non-reinforcing fillers.
  • the reinforcing fillers will allow advantageously to improve the mechanical properties of the silicone materials of the invention.
  • the fillers are preferably mineral. They can be especially siliceous.
  • the reinforcing siliceous fillers are chosen from precipitated or pyrogenic silicas, or mixtures thereof. These powders have an average particle size generally less than 0.1 ⁇ m (microns) and a BET specific surface area greater than 30 m 2 / g, preferably between 30 and 500 m 2 / g.
  • Semi-reinforcing siliceous fillers such as diatomaceous earth or ground quartz can also be used. In the case of non-siliceous minerals, they may 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 of between 0.001 and 300 ⁇ m (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 material according to the invention comprises fillers chosen from a quartz, a silica, in particular precipitated or pyrogenic silica and a calcium carbonate, alone or as a mixture.
  • the material of the present invention may comprise from 0.5 to 70% by weight of fillers, preferably from 1 to 60% by weight of filler, based on the weight of organopolysiloxane A.
  • the amount of filler in the material according to the invention may vary depending on the nature of the load. Those skilled in the art will be able to adapt the amount of charge depending on the nature of the charge and the desired properties.
  • the silicone material according to the invention can comprise: from 0.5 to 20%, preferably 1 to 15%, by weight of silica, in particular precipitated silica or fumed silica, relative to the weight of organopolysiloxane A, and / or
  • the silicone material according to the invention may further comprise:
  • organopolysiloxanes or branched (resins) chosen from nonfunctionalised organopolysiloxanes such as, for example, polydimethylsiloxanes and functionalized organopolysiloxanes such as, for example, polydimethylsiloxanes comprising hydroxyl, alkoxyl, alkenyl or piperidinyl groups; sterically hindered as described in EP 1758541.
  • crosslinking agent which is, for example, an organosilane or an organopolysiloxane having, by molecule, three hydrolyzable groups bonded to silicon,
  • a polycondensation catalyst selected from metal compounds based on tin, zinc, chromium, cobalt, nickel, titanium, aluminum, gallium, germanium or zirconium or organic compounds such as carbenes, amines, aminidines or guanidines .
  • one or more functional additives chosen in particular from:
  • Adhesion promoters or modulators are Adhesion promoters or modulators
  • the silicone material according to the invention are dynamic materials, that is to say that they have self-healing properties.
  • the self-healing of the materials according to the invention can be done by heating the material at a temperature between 50 and 130 ° C for 1 to 10 hours. For example by heating the material at 70 ° C for 48 hours.
  • the supramolecular silicone material according to the invention can also be recycled. Indeed, the inventors have shown that the materials according to the invention lose their mechanical properties when immersed. in hot water, especially at a temperature between 70 and 100 ° C for a long time, including 24 h to 167 h.
  • the supramolecular silicone material according to the invention is obtained by reaction between at least one organopolysiloxane A and at least one compound B.
  • the process for preparing the supramolecular silicone material preferably comprises the following steps:
  • the duration of the reaction at temperature depends on the nature of the reagents and the temperature. Those skilled in the art will be able to adjust the conditions of temperature and heating time to obtain materials having good mechanical and self-healing properties. As an indication, the reaction time at temperature can vary between a few hours at 100 ° C and a few days at 70 ° C.
  • step c) After step c) it is possible to put the resulting composition into shape in different ways, for example thin layer, in a mold or directly in a container. Step d) will come to create the ion network and generate the silicone material according to the invention.
  • the organic solvent S may especially be chosen from polar organic solvents, in particular alcohols, for example ethanol, or ethers, for example ethyl acetate or a mixture of these solvents.
  • the amount of organic solvent S used is low.
  • the amount of organic solvent S used in the process according to the invention is less than 30% by weight relative to the total weight of the mixture A + B + S, preferably less than 20%, and even more preferably less at 10%.
  • the silicone material of the invention comprises fillers
  • these may be introduced either directly in admixture with the organopolysiloxane A or in the reaction medium after mixing of the organopolysiloxane A and of the compound B.
  • the organopolysiloxane A according to the invention can be used pure (because of its molar mass of less than 70000 g / mol), in solution an organic solvent, for example S, or in emulsion.
  • the process of the invention is an emulsion process in which the organopolysiloxane A is emulsified in water.
  • the emulsion also comprises one or more surfactants or stabilizers, and the compound B is solubilized in water.
  • This emulsion may also contain other agents such as biocides, anti-gel additives, and / or anti-foam agents.
  • the present invention also relates to silicone materials as described above and comprising less than 50% by weight of organic solvent S, preferably less than 40% by weight, more preferably less than 30% by weight, in particular less than 20% by weight, preferably less than 10% by weight, for example less than 5% by weight, relative to the total weight of the silicone material.
  • Transparent and unstained materials or those with very low color are preferred.
  • the silicone materials according to the invention can in particular be used in the coating of flexible supports.
  • the flexible supports are chosen in particular from textiles, paper and polymer films.
  • the uses in textile coating relate for example to the production of airbag, conveyor belts, etc.
  • the uses in paper coating and polymer film relate to the production of anti-adhesive coatings.
  • Another application using the coating of polymer or textile films relates to the manufacture of dressings.
  • the invention therefore also covers a process for coating flexible supports comprising the use of the material according to the invention.
  • the silicone materials according to the invention can also be used for 3D printing.
  • the present invention also relates to the use of the silicone materials according to the invention, for the preparation of silicone elastomer articles by additive manufacturing processes also known as “3D printing” processes.
  • 3D printing processes also known as "3D printing” processes.
  • a "3D printer” is defined as “a machine used for 3D printing”
  • 3D printing is defined as "the manufacture of objects through the deposition of a material by means of a print head, a nozzle or other printer technology ".
  • additive manufacturing is defined as a process of joining materials to make objects from 3D model data, usually layer-by-layer, as opposed to subtractive manufacturing methods.
  • the synonyms associated with 3D printing and encompassed by 3D printing include additive manufacturing, additive processes, additive techniques and layer manufacturing.
  • Additive manufacturing (AM) can also be called rapid prototyping (RP).
  • RP rapid prototyping
  • additive manufacturing is interchangeable with “additive manufacturing” and vice versa.
  • the silicone materials according to the invention can be used for 3D printing processes involving the extrusion of material or the deposition of material.
  • Material extrusion is an additive manufacturing process in which a filament of material is extruded and selectively distributed through a nozzle.
  • the flow rate of extruded material can be controlled inter alia via the pressure exerted on the nozzle or the temperature.
  • Material deposition is an additive manufacturing process in which fine droplets of a material are selectively deposited by print heads similar to those of paper printers. This process is also known as inkjet or ink jet.
  • the present invention therefore also covers a 3D printing process comprising the implementation of a compound according to the invention.
  • the silicone materials according to the invention can also be used for water repellency of wood, concrete or stone.
  • the present invention thus also covers a method of water repellency of wood, concrete or stone comprising the implementation of a compound according to the invention.
  • the dynamic viscosity of the products was measured using an imposed stress rheometer (TA-DHRII). The measurements were performed in flow mode with a cone / plane geometry 40 mm in diameter and having a truncation of 52 ⁇ m. The viscosity was recorded as a function of shear rate (0.01 to 100 s 1) at 25 ° C.
  • the rheological analyzes were carried out using an imposed constraint rheometer
  • the tensile tests to determine the 100% deformation modulus, the tensile stress and the elongation at break were performed with a MTS 2 / M (10KN) uniaxial tensile machine.
  • the force cell has a maximum load of 100N.
  • a self-tightening jaw was used for the lower part and a pneumatic jaw for the upper part.
  • the specimens are of type H3.
  • An extensometer is used to measure elongation. The initial spacing is 10 mm.
  • the Shore 00 hardness and the Shore A hardness are measured with durometers over a thickness of 6.5 mm silicone material.
  • PDMS A21-A22-A23 Organic polysiloxane A according to the invention
  • a comparative example is also prepared from a PDMS A31 (Comparative Organopolysiloxane A):
  • organopolysiloxanes of general formula (V) below comprising methoxydimethylsiloxy end units, and D and T units, some of which comprise an aminoethylaminopropyl amino moiety.
  • This organopolysiloxane comprises more than two alkoxy functions.
  • the acid is solubilized in a mixture of 60% ethanol and 40% ethyl acetate.
  • the acid is concentrated in the solvent to about 1.5 mol / l.
  • the organopolysiloxane amine is introduced and cooled to about -20 ° C.
  • the acid solubilized in the solvent mixture is added so as to obtain the function ratio J described in the table.
  • reaction mixture is homogenized using a planetary mixer for about one minute at 2500 rpm.
  • reaction mixture After homogenization, the reaction mixture is poured into a petri dish or onto a tefloned plate and placed in an oven at 70 ° C. for 6 days.
  • the supramolecular material obtained is converted into a 1 mm thick film under pressure between 50 and 70 ° C. for 4 to 48 hours.
  • the materials of the invention have good mechanical properties. Comparison between materials according to the invention and materials obtained with oraanopolysiloxanes comprising more than two alkoxy units, the acid being citric acid.
  • organopolysiloxane A used is A23 and the acid B is citric acid.
  • healing is provided by the temperature (heating at 70 ° C. for 48 hours). In the two examples below, it is shown that after healing, a major part of the mechanical properties is recovered.
  • the materials according to the invention lose their mechanical properties when immersed in water at 70 ° C for 7 days. This experiment shows that the material can be recycled via this aqueous route.
  • Comparative Example 6 Organicpolysiloxane comprising more than two alkoxy units
  • Comparative Example 6 Organicpolysiloxane comprising more than two alkoxy units

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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EP19706704.4A 2018-02-28 2019-02-27 Silikonmaterialien Pending EP3759186A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1851779A FR3078335B1 (fr) 2018-02-28 2018-02-28 Materiaux silicones
PCT/EP2019/054893 WO2019166507A1 (fr) 2018-02-28 2019-02-27 Matériaux silicones

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EP3759186A1 true EP3759186A1 (de) 2021-01-06

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JP (1) JP6991350B2 (de)
KR (1) KR102482180B1 (de)
CN (1) CN111819255B (de)
FR (1) FR3078335B1 (de)
WO (1) WO2019166507A1 (de)

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FR3078335B1 (fr) 2018-02-28 2020-12-25 Elkem Silicones France Sas Materiaux silicones
JP2020063407A (ja) * 2018-10-19 2020-04-23 メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ ポリシロキサン組成物
KR20220040925A (ko) 2020-09-24 2022-03-31 삼성전자주식회사 힌지 구조물 및 이를 포함하는 전자 장치
CN116987278A (zh) * 2023-08-04 2023-11-03 浙江永通新材料股份有限公司 一种低温可自愈合聚硅氧烷超分子弹性体及其制备方法

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Publication number Priority date Publication date Assignee Title
US4246423A (en) * 1979-10-22 1981-01-20 Sws Silicones Corporation Silicone polyether copolymers
US4915938A (en) * 1987-11-13 1990-04-10 Zawadzki Mary E Hair treating composition
JPH03254571A (ja) 1990-03-05 1991-11-13 Ricoh Co Ltd 画像形成装置
US6124490A (en) 1999-10-26 2000-09-26 Mona Industries, Inc. Zwitterionic siloxane polymers and ionically cross-linked polymers formed therefrom
FR2872038A1 (fr) 2004-06-23 2005-12-30 Rhodia Chimie Sa Composition cosmetique comprenant un polyorganosiloxane et ses utilisations
KR101292028B1 (ko) * 2005-06-21 2013-08-01 다우 코닝 도레이 캄파니 리미티드 변형된 오가노폴리실록산을 포함하는 화장품
FR3030536B1 (fr) 2014-12-22 2018-06-15 Institut National Des Sciences Appliquees Lyon Organopolysiloxanes et leur procede de preparation
US9982223B2 (en) * 2015-01-28 2018-05-29 The Procter & Gamble Company Amino silicone nanoemulsion
CN105111470B (zh) * 2015-08-13 2017-12-01 四川大学 一种可逆共价交联聚硅氧烷弹性体及其制备方法与应用
FR3052784A1 (fr) * 2016-06-21 2017-12-22 Bluestar Silicones France Procede de lutte contre l'apparition de brouillard dans un dispositif a cylindres lors de l'enduction de supports flexibles avec une composition silicone liquide reticulable
FR3078335B1 (fr) 2018-02-28 2020-12-25 Elkem Silicones France Sas Materiaux silicones

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FR3078335B1 (fr) 2020-12-25
KR20200124239A (ko) 2020-11-02
US20210071033A1 (en) 2021-03-11
US11945965B2 (en) 2024-04-02
JP2021517918A (ja) 2021-07-29
CN111819255B (zh) 2022-01-11
CN111819255A (zh) 2020-10-23
JP6991350B2 (ja) 2022-01-14
WO2019166507A1 (fr) 2019-09-06
FR3078335A1 (fr) 2019-08-30
KR102482180B1 (ko) 2022-12-28

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