WO2025133480A1 - Polyaddition-crosslinkable silicone composition for preparing thermally conductive silicone elastomer - Google Patents
Polyaddition-crosslinkable silicone composition for preparing thermally conductive silicone elastomer Download PDFInfo
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- WO2025133480A1 WO2025133480A1 PCT/FR2024/000122 FR2024000122W WO2025133480A1 WO 2025133480 A1 WO2025133480 A1 WO 2025133480A1 FR 2024000122 W FR2024000122 W FR 2024000122W WO 2025133480 A1 WO2025133480 A1 WO 2025133480A1
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- 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
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- 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
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- 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
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
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- 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
Definitions
- TITLE Poly-addition crosslinkable silicone composition for the preparation of thermally conductive silicone elastomer
- the present invention relates to new silicone compositions crosslinking by polyaddition reaction, intended to produce thermally conductive elements in particular for the electronics and automotive fields, in particular for the field of electric vehicles.
- Thermally conductive silicone elastomers are well known for their remarkable heat transfer properties, thermal resistance to heat and cold, and electrical insulation. They are used in particular in electrical and electronic applications, and in the automotive field. Particularly in the automotive field, thermally conductive silicone elastomers are used in the batteries of electric vehicles and hybrid vehicles (EV and HEV) to evacuate heat from battery pack cells and on-board electronics.
- EV and HEV electric vehicles and hybrid vehicles
- Thermally conductive silicone formulations have been described in the prior art. As early as 1981, US Patent 4,292,223 described thermally conductive elastomers comprising organopolysiloxanes, a particulate filler and a viscosity modifier.
- thermally conductive filler in silicone compositions is high, typically greater than 50% by weight, or even greater than 70% by weight.
- One of the challenges in designing thermally conductive silicones lies in adding such large amounts of thermally conductive fillers while minimizing the impact on the fluidity of the composition. This is particularly critical for so-called “potting” compositions, whose viscosity must be low, typically less than
- thermally conductive silicone compositions Several solutions have been proposed in the prior art to control the viscosity of thermally conductive silicone compositions.
- One method consists of carefully choosing the type of filler, its shape and its size.
- application WO 2021/260279 A1 from Elkem Silicones proposes the selection of certain fillers having specific dimensions, with a ratio to be respected between large and small particles.
- Patent EP 1 788 031 B1 from Shin-Etsu Chemical describes a thermally conductive silicone elastomer comprising, per 100 parts by weight of a heat-crosslinkable organopolysiloxane composition, from 10 to 2000 parts by weight of a metallic silicon powder having an average particle size of less than 100 ⁇ m.
- Another method consists of changing the medium of the silicone formulation or adding a solvent.
- thermally conductive fillers so as to improve their compatibility with the silicone matrix.
- international patent application WO 2023/283819 A1 filed by Dow Silicones and Dow Global Technologies, describes a self-adhesive thermally conductive silicone composition comprising in particular a thermally conductive filler and a treatment agent, in combination with an adhesion promoting agent containing at the same time a hydrogen atom bonded to a silicon atom and at least one alkoxy group bonded to a silicon atom.
- an adhesion promoting agent containing at the same time a hydrogen atom bonded to a silicon atom and at least one alkoxy group bonded to a silicon atom.
- the addition of a treatment agent in the formulation can have negative impacts on the mechanical properties of the silicone elastomer, and phenomena of exudation of the treatment agents from the silicone matrix are noted.
- terminal units M and M V1 include trimethylsiloxy, dimethylphenylsiloxy, dimethylvinylsiloxy or dimethylhexenylsiloxy groups.
- the content of T-type siloxyl unit in the organopolysiloxane compound A is a mass content, representing the weight of the T unit “S i O3/2”, relative to the total of the organopolysiloxane compound A. It can be measured, in a manner known to those skilled in the art, by any appropriate assay method. Alternatively, it can be calculated theoretically by taking into account the mass of T units introduced into the reaction medium during the synthesis of the organopolysiloxane A.
- Organopolysiloxane A can have the following general average formula: [YR'zSiOi/zla [R SiOi/zlb [R 1 2 SiO 2 /2]c [R 1 SiO 3/2 ]d in which
- - Y represents a C2-C12 alkenyl group, preferably a vinyl group
- the organopolysiloxane A may have a residual acidity content.
- the residual acidity content may be greater than or equal to 5 ppm, preferably between 6 ppm and 100 ppm, and more preferably between 10 ppm and 100 ppm.
- the presence of a residual acidity greater than or equal to 5 ppm, preferably between 6 ppm and 100 ppm, in the organopolysiloxane A could make it possible to reduce the viscosity of the silicone composition crosslinkable by polyaddition reaction according to the present invention and to improve its thixotropic index.
- organopolysiloxane A does not have, or does not significantly have, residual acidity.
- the residual acidity content may be strictly less than 5 ppm, preferably less than 4 ppm, and more preferably less than 3 ppm.
- the inventors believe that the absence of significant residual acidity in organopolysiloxane A has the advantage of improving the stability over time of said organopolysiloxane, in particular at high temperature.
- the silicone composition crosslinkable by polyaddition reaction according to the present invention can have better stability over time and a longer storage life.
- the organopolysiloxane A according to the invention can be selected from commercially available compounds meeting the stated specifications. Alternatively, it can be synthesized according to methods known in the technical field.
- organopolysiloxane A is obtained by ring-opening polymerization (ROP) in the presence of nucleophilic or electrophilic initiators.
- ROP ring-opening polymerization
- These synthesis methods are well known to those skilled in the art and are for example described in the article “Ring-Opening Polymerization (ROP) and Catalytic Rearrangement as a Way to Obtain Siloxane Mono- and Telechelics, as Well as Well-Organized Branching Centers: History and Prospects”, Bezlepkina et al, Polymers 2022, 14, 2408. These methods make it possible to effectively control the molecular weight of the polymer by selecting the amount of initiator and the amount of chain blockers.
- organopolysiloxane A can be carried out by anionic polymerization or by cationic polymerization.
- the initiator may be chosen from nucleophilic catalysts well known to those skilled in the art.
- the initiator may be chosen from acid catalysts well known to those skilled in the art.
- organopolysiloxanes having alkenyl (preferably vinyl) groups in terminal positions.
- the synthesis of organopolysiloxane A according to the present invention can therefore be carried out from cyclic oligosiloxanes, typically hexamethylcyclotrisiloxane (D3) or octamethylcyclotetrasiloxane (D4), and alkenyl, preferably vinyl, chain blockers, typically divinyldimethyldisiloxane (M V1 2).
- the content of T-type Si-Os/2 siloxyl unit can be controlled by adding a source of T-type siloxyl unit during synthesis.
- This source of T-type siloxyl unit can be chosen from a branched organopolysiloxane containing T-type siloxyl units or a silane compound carrying at least one T-unit.
- the source of T-type siloxyl unit is a branched organopolysiloxane containing T-type siloxyl units, preferably a silicone resin having a low molecular weight and/or low viscosity.
- the source of T-type siloxyl unit is a silane compound carrying at least one T-unit, preferably a silane compound of formula R 3 Si(OR 4 )s, in which R 3 represents a group monovalent hydrocarbon having from 1 to 16 carbon atoms, preferably chosen from alkyl groups having from 1 to 8 carbon atoms such as methyl, ethyl, propyl groups, cycloalkyl groups having from 3 to 8 carbon atoms and aryl groups having from 6 to 12 carbon atoms; and each R 4 represents, independently of one another, a monovalent hydrocarbon group having from 1 to 16 carbon atoms, preferably selected from alkyl groups having from 1 to 8 carbon atoms such as methyl, ethyl, propyl groups, cycloalkyl groups having from 3 to 8 carbon atoms and aryl groups having from 6 to 12 carbon atoms, C2-C1 alkenyl groups, such as the vinyl group, and -Si(R 5 )
- the source of T-type siloxyl unit is a silane compound carrying at least one of the T unit, preferably a silane compound of formula R 3 Si(OR 4 )s, in which R 3 represents a monovalent hydrocarbon group having from 1 to 16 carbon atoms; and each R 4 represents, independently of each other, a monovalent hydrocarbon group having from 1 to 16 carbon atoms.
- the content of silicon-bonded OH groups can be controlled by adding a source of OH groups during the synthesis.
- This source of OH groups can be chosen from: an ⁇ , ⁇ -dihydroxylated oligo-organosiloxane, an ⁇ , ⁇ -dihydroxylated polyorganosiloxane, Silox, a hydroxylated silicone resin, or water.
- Said ⁇ , ⁇ -dihydroxylated oligo- and polyorganosiloxanes are preferably chosen from those having a low molecular weight, preferably less than 20,000 g/mol, more preferably less than 15,000 g/mol (weight-average molar mass), and/or low viscosity, preferably less than 1,000 mPa.s.
- the term "Silox” refers to mixtures of ⁇ , ⁇ -dihydroxylated oligo- or polyorganosiloxane and cyclosiloxanes. These mixtures are obtained from the direct synthesis of organochlorosilanes (Rochow synthesis) and the hydrolysis of the resulting chlorosilanes.
- the silicone composition preferably comprises from 5% to 50% by weight of organopolysiloxane A, even more preferably from 10% to 40% by weight of organopolysiloxane A.
- Q siloxyl unit SiC>4/2, with R 2 representing a monovalent radical having from 1 to 12 carbon atoms.
- Organopolysiloxane B is an organopolysiloxane having, per molecule, at least two SiH units. It is therefore an organohydrogenopolysiloxane compound. Preferably, organopolysiloxane B comprises at least three SiH units.
- R 2 may represent a monovalent radical chosen from the group consisting of alkyl groups having 1 to 8 carbon atoms, optionally substituted by at least one halogen atom such as chlorine or fluorine, cycloalkyl groups having from 3 to 8 carbon atoms and aryl groups having from 6 to 12 carbon atoms.
- R 2 may advantageously be chosen from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl.
- the symbol d is preferably equal to 1.
- Organopolysiloxane B may have a linear, branched, or cyclic structure.
- the degree of polymerization is preferably greater than or equal to 2. Generally, it is less than 5000.
- the viscosity of organopolysiloxane B is between 1 mPa.s and 5000 mPa.s, more preferably between 1 mPa.s and 2000 mPa.s, and even more preferably between 5 mPa.s and 1000 mPa.s.
- organohydrogenpolysiloxanes which may be organopolysiloxanes B according to the invention are:
- organopolysiloxane B has a branched structure, it is preferably chosen from the group consisting of silicone resins of the following formulae:
- the organopolysiloxane B has a mass content of hydrogenosilyl Si-H functions of between 0.2% and 91%, more preferably between 3% and 80% and even more preferably between 15% and 70%.
- the silicone composition according to the invention preferably comprises 0.1% to 15% by weight, and more preferably from 0.5% to 10% by weight, of organopolysiloxane B.
- the silicone composition according to the invention may comprise an organopolysiloxane B or a mixture of several organopolysiloxanes B, for example a mixture of a poly(dimethylsiloxane) with hydrogenodimethylsilyl ends and of organopolysiloxane having, per molecule, at least three SiH units.
- the molar ratio of the hydrogenosilyl functions Si-H of the organopolysiloxanes B to the alkene functions of the organopolysiloxanes A is between 0.2 and 10, preferably between 0.5 and 5.
- the polyaddition catalyst C may in particular be chosen from platinum and rhodium compounds but also from silicon compounds such as those described in patent applications WO 2015/004396 and WO 2015/004397, germanium compounds such as those described in patent application WO 2016/075414, nickel, cobalt or iron complexes such as those described in patent applications WO 2016/071651, WO 2016/071652, WO 2016/071654, WO 2018/115601, WO 2019/008279, WO 2019/138194, WO 2023/031524 and WO 2023/031525, or manganese complexes such as those described in applications WO 2023/139322 and WO 2024/146993.
- Catalyst C is preferably a compound derived from at least one metal belonging to the platinum group. These catalysts are well known. In particular, it is possible to use the complexes of platinum and an organic product described in US patents 3,159,601, US 3,159,602, US 3,220,972 and European patents EP 0.057.459, EP 0.188.978 and EP 0.190.530, the complexes of platinum and of vinyl organosiloxanes described in US patents 3,419,593, US 3,715,334, US 3,377,432 and US 3,814,730.
- a polyaddition photocatalyst may be used.
- Such a catalyst may be activated by irradiation, preferably by UV irradiation.
- a platinum-based photocatalyst may be selected, for example, from: platinum bis(acetylacetonate), platinum trimethyl(acetylacetonate), platinum trimethyl(2,4-pentanedione), platinum trimethyl(3,5-heptanedione), platinum trimethyl(methyl acetoacetate), platinum bis(2,4-pentanedione), platinum bis(2,4-hexanedione), platinum bis(2,4-heptanedione), platinum bis(3,5-heptanedione) and platinum bis(1-phenyl-1,3-butanedione).
- catalyst C is a compound derived from platinum.
- the weight quantity of catalyst C calculated as the weight of platinum metal, is generally between 2 ppm and 400 ppm by mass, preferably between 5 ppm and 200 ppm, based on the total weight of the silicone composition.
- catalyst C is a Karstedt platinum.
- the silicone composition crosslinkable by polyaddition reaction according to the present invention is characterized in particular by the fact that it comprises a thermally conductive filler D.
- a thermally conductive filler D This may consist of a single filler or a mixture of fillers having a different chemical nature and/or a different structure and/or a different particle size.
- the thermally conductive filler D consists of a mixture of at least two fillers or at least three fillers having a different chemical nature and/or a different particle size.
- the thermally conductive filler D consists of a single filler.
- the total weight of the thermally conductive filler D in the silicone composition crosslinkable by polyaddition reaction is preferably greater than 50%, more preferably greater than 60%, and even more preferably between 70% and 95%, by weight relative to the total weight of the silicone composition crosslinkable by polyaddition reaction.
- the thermally conductive filler D may contain one or more fillers of different nature known to those skilled in the art for their thermally conductive properties, in particular among metals, alloys, metal oxides, metal hydroxides, metal nitrides, metal carbides, metal silicides, carbon, soft magnetic alloys and ferrites.
- the thermal conductivity of these fillers is preferably greater than 10 W/mK, more preferably greater than 20 W/mK, and even more preferably greater than 50 W/mK.
- the thermally conductive filler D may comprise a thermally conductive filler selected from the group consisting of an alumina filler, an aluminum trihydrate (ATH) filler, an aluminum filler, a silica filler, a metallic silicon filler, a zinc oxide filler, an aluminum nitride filler, a boron nitride filler, and mixtures thereof.
- the thermally conductive filler D may comprise a thermally conductive filler selected from the group consisting of an alumina filler, an aluminum trihydrate (ATH) filler, a zinc oxide filler, a silica filler, and mixtures thereof.
- a thermally conductive filler selected from the group consisting of an alumina filler, an aluminum trihydrate (ATH) filler, a zinc oxide filler, a silica filler, and mixtures thereof.
- the thermally conductive filler D may have any shape known to those skilled in the art, for example a spherical shape, a needle shape, a disc shape, a rod shape, or an indefinite shape.
- the thermally conductive filler has a spherical shape or an indefinite shape.
- these may have the same shape or different shapes.
- the thermally conductive filler(s) may be used as such or may be surface treated. Said surface treatment typically aims to improve the dispersibility of the filler in the organopolysiloxane composition and/or to improve the thermal stability of the composition. In addition, the heat treatment may improve the physical stability of the composition, by avoiding settling or exudation phenomena, or even an increase in viscosity.
- Said surface treatment may be a heat treatment, a chemical treatment, a physical treatment, or their combinations, in particular the combination of a heat treatment and a chemical treatment.
- the thermally conductive filler can be treated with organosilicon compounds usually used for this purpose.
- the silicone composition crosslinkable by polyaddition reaction according to the invention can therefore comprise an agent for treating the thermally conductive filler.
- agents include:
- organosiloxanes in particular methylpolysiloxanes such as hexamethyldisiloxane and
- organosilazanes in particular methylpolysilazanes such as hexamethyldisilazane, divinyltetramethyldisilazane and hexamethylcyclotrisilazane,
- chlorosilanes such as dimethyldichlorosilane, trimethylchlorosilane, methylvinyldichlorosilane and dimethylvinylchlorosilane,
- - alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, a (C6-C8)alkyltrimethoxysilane such as octyltrimethoxysilane, vinyltrimethoxysilane, dimethylvinylethoxysilane, vinyltri(2-methoxyethoxy)silane, vinyltriacetoxysilane,
- the thermally conductive filler may be treated with an alkoxysilane, especially a (C6-C8)alkyltrimethoxysilane, or with an organosilazane, especially hexamethyldisilazane (HMDZ) and divinyltetramethyldisilazane, or a mixture thereof, especially a mixture of HMDZ and divinyltetramethyldisilazane.
- HMDZ hexamethyldisilazane
- divinyltetramethyldisilazane or a mixture thereof, especially a mixture of HMDZ and divinyltetramethyldisilazane.
- water may typically be added.
- the silicone composition crosslinkable by polyaddition reaction according to the invention preferably comprises from 0.05% to 5% of a heat-conducting filler treatment agent, and more preferably from 0.1% to 3% by weight, relative to the total weight of the silicone composition crosslinkable by polyaddition reaction according to the invention.
- a heat treatment of the thermally conductive charge may consist of subjecting said charge to a temperature between 70°C and 200°C for a period between 1 hour and 4 hours.
- the surface treatment can be carried out before the incorporation of the thermally conductive filler into the silicone composition.
- the treatment of the thermally conductive filler can be carried out in situ, during the preparation of the silicone composition.
- the silicone composition crosslinkable by polyaddition reaction according to the invention may also comprise other compounds, in particular:
- At least one mineral filler in particular silica, quartz, or a mixture of these;
- the silicone composition comprises a mineral filler E, which is preferably a combustion silica or a precipitation silica.
- the silica-type mineral fillers preferably have a specific surface area, measured according to BET methods, of at least 10 m 2 /g, in particular between 10 m 2 /g and 400 m 2 /g, an average primary particle size of less than 0.1 pm (micrometer) and an apparent density of less than 200 g/liter.
- the mineral filler E is a combustion silica whose specific surface area is between 10 m 2 /g and 300 m 2 /g.
- silica-type mineral fillers preferably hydrophilic
- these silicas may optionally be treated with one or more organosilicon compounds, for example organosilane or organosilazane, usually used for this purpose.
- methylpolysiloxanes such as hexamethyldisiloxane, octamethylcyclo-tetrasiloxane, methylpolysilazanes such as hexamethyldisilazane, hexamethylcyclotrisilazane, tetramethyldivinyldisilazane, chlorosilanes such as dimethyldichlorosilane, trimethylchlorosilane, methylvinyldichlorosilane, dimethylvinylchlorosilane, alkoxysilanes such as dimethyldimethoxysilane, dimethylvinylethoxy silane, trimethylmethoxysilane.
- These compounds can be used alone or in mixtures (see French patents FR 1 126 884, FR 1 136 885, FR 1 236 505 and English patent GB 1 024 234).
- the silica may optionally be pre-dispersed in a silicone oil, so as to obtain a suspension. It is particularly preferred to use a suspension of treated combustion silica, in particular with hexamethyldisilazane, in a polyorganosiloxane oil, in particular vinylated.
- the silicone composition according to the invention may also contain at least one other mineral filler which is quartz.
- a ground natural quartz with an average particle size of less than 10 microns is used.
- the quartz may optionally be treated to improve its compatibility with organopolysiloxanes.
- mineral fillers may be considered, including bulking fillers, such as diatomaceous earth, calcium carbonate and/or kaolin.
- the silicone composition crosslinkable by polyaddition reaction according to the invention may optionally comprise a crosslinking inhibitor F.
- the function of the inhibitor F is to slow down the polyaddition reaction.
- the crosslinking inhibitor F may be chosen from the following compounds:
- organopolysiloxane advantageously cyclic, and substituted by at least one alkenyl, tetramethyltetravinylcyclotetrasiloxane being particularly preferred,
- R 1 is a linear or branched alkyl radical, or a phenyl radical
- R 2 is a hydrogen atom, a linear or branched alkyl radical, or a phenyl radical,
- R 1 and R 2 the total number of carbon atoms contained in R 1 and R 2 being at least 5, preferably from 9 to 20.
- Said acetylenic alcohols are preferably chosen from those having a boiling point above 250°C. Examples include the following products which are commercially available: 1-ethynyl-1-cyclohexanol, methyl-3-dodecyne-1-ol-3, trimethyl-3,7,11- dodecyne-1-ol-3, diphenyl-1,1-propyne-2-ol-1, ethyl-3-ethyl-6-nonyne-1-ol-3 and methyl-3-pentadecyne-1-ol-3.
- the crosslinking inhibitor F is 1-ethynyl-1-cyclohexanol or tetramethyltetravinylcyclotetrasiloxane.
- the presence of the inhibitor may or may not be necessary. If necessary, such a crosslinking inhibitor may typically be present at a maximum of 3000 ppm, preferably at a maximum of 100 ppm to 2000 ppm relative to the total weight of the silicone composition crosslinkable by polyaddition reaction according to the invention.
- the silicone composition crosslinkable by polyaddition reaction according to the invention may optionally comprise a non-reactive organopolysiloxane which is liquid at room temperature G.
- the non-reactive organopolysiloxanes which are liquid at room temperature have the function of reducing the overall viscosity of the composition.
- non-reactive means that this organopolysiloxane does not participate in the polyaddition reaction leading to the crosslinking of the elastomer.
- said non-reactive organopolysiloxane liquid at room temperature G is a linear diorganopolysiloxane blocked at each end of its chain by a triorganosiloxy unit, the organic radicals of which linked to the silicon atoms are chosen from alkyl radicals having from 1 to 8 carbon atoms. It may typically be a polydimethylsiloxane with trimethylsiloxy terminations.
- the non-reactive organopolysiloxane liquid at room temperature G preferably has a viscosity of between 50 mPa and 1,000 mPa.s, preferably between 50 mPa.s and 500 mPa.s, more preferably between 50 mPa.s and 200 mPa.s.
- the dynamic viscosity is measured at 25 °C in a manner known per se, with a Brookfield viscometer at a shear rate gradient sufficiently low so that the measured viscosity is independent of the rate gradient.
- the silicone composition crosslinkable by polyaddition reaction according to the invention comprises (by weight relative to the total weight of the silicone composition) from 0% to 10%, preferably from 0.1% to 5%, of a non-reactive organopolysiloxane liquid at room temperature G.
- the silicone composition crosslinkable by polyaddition reaction according to the present invention may optionally comprise other additives traditionally used in this technical field by those skilled in the art, for example an adhesion promoter, a colorant, a fire retardant, a rheological agent such as a thixotropic agent, etc.
- additives traditionally used in this technical field by those skilled in the art, for example an adhesion promoter, a colorant, a fire retardant, a rheological agent such as a thixotropic agent, etc.
- the silicone composition crosslinkable by polyaddition reaction according to the present invention may contain a low level of volatile organic compounds, typically less than 100 pgC/g, preferably less than 70 pgC/g, or even less than 50 pgC/g.
- the organopolysiloxane compounds used in the composition according to the present invention may be preferably chosen from compounds themselves containing a low level of volatile organic compounds.
- the silicone composition crosslinkable by polyaddition reaction according to the invention comprises (by weight relative to the total weight of the silicone composition):
- the silicone composition crosslinkable by polyaddition reaction according to the invention comprises (by weight relative to the total weight of the silicone composition):
- the silicone composition crosslinkable by polyaddition reaction according to the invention comprises (by weight relative to the total weight of the silicone composition):
- a crosslinking inhibitor F from 100 ppm to 2000 ppm of a crosslinking inhibitor F, and - from 0% to 10%, preferably from 0.1% to 5%, of a non-reactive organopolysiloxane liquid at room temperature G.
- the silicone composition according to the invention can be prepared from a two-component (or multi-component) system characterized in that it is present in two (or more) distinct parts intended to be mixed to form said silicone composition.
- the silicone composition can be prepared from a two-component system characterized in that one of the parts comprises catalyst C and does not comprise organopolysiloxane B, while the other part comprises organopolysiloxane B and does not comprise catalyst C.
- Other multi-component systems can be provided to improve the storage life and/or optimize the viscosity of each of the components.
- the silicone composition according to the invention can be prepared from a three-component system characterized in that it is present in three distinct parts intended to be mixed to form said silicone composition.
- the silicone composition according to the invention is presented in two distinct parts PI and P2 intended to be mixed to form said silicone composition, the part PI comprising:
- organopolysiloxane A having, per molecule, at least one C2-C12 alkenyl group linked to silicon
- part P2 comprising:
- organopolysiloxane A having, per molecule, at least one C2-C12 alkenyl group linked to silicon
- organopolysiloxane B having, per molecule, at least two SiH units
- thermally conductive filler D all or part of the thermally conductive filler D, optionally with the thermally conductive filler treatment agent
- the thermally conductive filler D can be present in part PI, in part P2 or in both parts PI and P2, with identical or different contents between parts PI and P2.
- the thermally conductive filler D may be present in the PI part and in the P2 part in an identical content.
- the total content of thermally conductive filler D remains invariable in the silicone composition crosslinkable by polyaddition reaction regardless of the mixing rate of the PI and P2 parts.
- Each of the PI and P2 parts according to the present invention may be obtained by mixing the different components in a suitable device known to those skilled in the art.
- the part PI, the part P2 or both parts PI and P2 can be obtained from an intermediate composition comprising all or part of the organopoly siloxane A and all or part of the thermally conductive filler D, as well as optionally the agent for treating the thermally conductive filler.
- the present invention also relates to the silicone elastomer obtained or capable of being obtained by crosslinking the crosslinkable silicone composition by polyaddition reaction as defined above, the process for obtaining said elastomer, as well as the use of said elastomer.
- the silicone composition crosslinkable by polyaddition reaction as defined above is particularly suitable for the preparation of a silicone elastomer having thermoconductive properties.
- An object of the present invention consists of a process for preparing a thermally conductive silicone elastomer comprising the step of allowing said crosslinkable silicone composition to crosslink by polyaddition reaction to obtain said thermally conductive silicone elastomer.
- Another object of the present invention consists of a process for preparing a silicone elastomer comprising the following steps: a) providing a two-component system comprising all the components of the silicone composition crosslinkable by polyaddition reaction as defined above; b) mixing the two parts of said two-component system to obtain the silicone composition crosslinkable by polyaddition reaction; and c) allowing said silicone composition crosslinkable by polyaddition reaction to crosslink to obtain said thermally conductive silicone elastomer.
- the crosslinking step can have a variable duration depending on the silicone composition and the temperature. Generally, a silicone elastomer with good properties is obtained after a few minutes or a few hours depending on the temperature and the concentration of catalyst and inhibitor in the silicone composition.
- the mixing of the parts of the two-component (or multi-component) system can typically take place in a mixer (mechanical stirrer with inclined blades, low-pressure dynamic mixer, or any other conventional stirring system) at a temperature close to room temperature, i.e. between 10°C and 40°C. An increase in the temperature of the silicone composition is sometimes observed during this mixing depending on the type of mixer and the shear applied. If it is desired to accelerate the crosslinking of the silicone composition, the mixing can be carried out at a higher temperature, advantageously between 40°C and 70°C.
- Said silicone elastomer can advantageously be used as a thermally conductive material in various technical fields, in particular in the field of electronics, in electrical applications, and in the automotive field.
- Said silicone elastomer can advantageously be used as a thermally conductive potting material (i.e. "potting” according to English terminology), filling material (i.e. "gap-filler” according to English terminology) or adhesive thermally conductive material, in particular for batteries, for example batteries of electric vehicles and hybrid vehicles, but also stationary batteries.
- the present invention also relates to a battery, preferably an electric vehicle or hybrid vehicle battery, comprising the thermally conductive silicone elastomer which is the subject of the present invention as a thermally conductive potting material, filling material or adhesive thermally conductive material.
- the silicone elastomer according to the invention can advantageously be used as a thermally conductive material in 5G devices.
- the silicone composition crosslinkable by polyaddition reaction according to the present invention as well as the parts PI and P2 of the two-component system P precursor of the silicone composition crosslinkable by polyaddition reaction, have good processability. Indeed, despite the presence of a high content of thermally conductive filler, said compositions advantageously remain sufficiently fluid to be easily handled, in particular extrudable.
- organopolysiloxane A allowing to lower the viscosity at 25°C to one at a shear rate of 10 s 1 (which can be described as high shear) or 1 s 1 (which can be described as low shear), as well as to lower the thixotropic index.
- the silicone elastomer which is the subject of the present invention, obtained or capable of being obtained by crosslinking the crosslinkable silicone composition by polyaddition reaction advantageously has a thermal conductivity of between 0.5 W/m.K and 7 W/m.K, preferably of between 0.9 W/m.K and 5 W/m.K, more preferably of between 1 W/m.K and 3 W/m.K.
- A1 to A8 End-vinyl polydimethylsiloxane oils whose specifications are given in tables 2 to 5.
- the T units were added to oils A3 to A6 by controlled addition of a silicone resin containing T-type siloxyl units.
- the T units were added to oils A7 and A8 by controlled addition of hexadecyltrimethoxysilane.
- C Karstedt platinum catalyst, containing 10% by weight of platinum metal
- Viscosity of silicone oils A measured on a Brookfield rotary viscometer (needle no. 1) at a speed of 500 rpm at 25 °C.
- Viscosity of silicone compositions measured on a Haake rheometer at 25 °C, following a program using an upward and downward shear ramp, from 0 s 1 to 20 s 1 in 120 s ( 1st part) then from 20 s 1 to 0 s 1 in 120 s ( 2nd part).
- the viscosity values recorded are the values at 10 s 1 and 1 s 1 obtained during the 2nd part of the program (decreasing ramp).
- the installation used is of plane/plane geometry.
- the diameter of the upper plate is 20 mm.
- the distance between the two plates is 0.500 mm.
- T-type siloxyl unit content ([T]):
- the T-type siloxyl unit content in the organopolysiloxane compound A is a content by weight of SiO3/2 units, relative to the total weight (weight of T-unit “SiOs/2” /total weight of the polydimethylsiloxane oil A).
- the value indicated in the examples below is a theoretical value calculated from the respective quantities of raw materials used during the synthesis of the polydimethylsiloxane oils A1 to A8.
- the silicon-bonded OH content was measured by infrared, according to the deuterated method described in “Measurement of Trace Silanol in Siloxanes by IR Spectroscopy” by Elmer D. Lipp, Applied Spectroscopy vol. 45, no. 3, 1991, pp. 477-483. In practice, the calibration curve was constructed from standard solutions with known OH content. The OH content of the sample was calculated by measuring the optical density of the second derivative of the SiOD band at 2726 cm' 1 .
- compositions 1 - 13 Compositions 1 - 13:
- Silicone compositions corresponding to parts PI and P2 were prepared according to the following protocol: For part PI: the thermally conductive filler D, the silicone oil A, the filler E, the coloring base and the catalyst C were mixed according to the concentration indicated in table 1 below. below. For part P2: thermally conductive filler D, silicone oil A, silicone oils B1 and B2, filler E and a retarder F were mixed according to the concentration indicated in Table 1 below.
- compositions were thus obtained with different vinylated polydimethylsiloxane oils chain end A1 to A5.
- the results of the analyses on the PI parts are given in Table 2.
- the results of the analyses for the P2 parts are given in Table 3.
- 100 ppm advantageously reduces the viscosity of the PI and P2 parts of the composition. This effect seems to be reinforced by the presence of OH groups in oil A. On the PI part, the use of an oil A with a siloxyl unit T content greater than 100 ppm also reduces its thixotropic index.
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Abstract
Description
DESCRIPTION DESCRIPTION
TITRE : Composition silicone réticulable par poly addition pour la préparation d’élastomère silicone thermoconducteur TITLE: Poly-addition crosslinkable silicone composition for the preparation of thermally conductive silicone elastomer
Domaine technique Technical field
La présente invention concerne de nouvelles compositions silicones réticulant par réaction de polyaddition, destinées à produire des éléments thermoconducteurs notamment pour le domaine de l’électronique et de l’automobile, en particulier pour le domaine des véhicules électriques. The present invention relates to new silicone compositions crosslinking by polyaddition reaction, intended to produce thermally conductive elements in particular for the electronics and automotive fields, in particular for the field of electric vehicles.
Etat de la technique antérieure State of the prior art
Les élastomères silicones thermoconducteurs sont bien connus pour leurs propriétés remarquables de transfert de chaleur, de résistance thermique au chaud et au froid, et d’isolation électrique. Ils sont utilisés notamment dans les applications électriques et électroniques, et dans le domaine automobile. En particulier dans le domaine automobile, les élastomères silicones thermoconducteurs sont utilisés au niveau des batteries des véhicules électriques et des véhicules hybrides (« EV » et « HEV » selon la terminologie anglo-saxonne) pour évacuer la chaleur des cellules des blocs-batteries et de l’électronique embarquée. Thermally conductive silicone elastomers are well known for their remarkable heat transfer properties, thermal resistance to heat and cold, and electrical insulation. They are used in particular in electrical and electronic applications, and in the automotive field. Particularly in the automotive field, thermally conductive silicone elastomers are used in the batteries of electric vehicles and hybrid vehicles (EV and HEV) to evacuate heat from battery pack cells and on-board electronics.
Des formulations de silicones thermoconductrices ont été décrites dans l’art antérieur. Dès 1981, le brevet US 4,292,223 décrivait des élastomères thermoconducteurs comprenant des organopolysiloxanes, une charge particulaire et un modifiant de viscosité. Thermally conductive silicone formulations have been described in the prior art. As early as 1981, US Patent 4,292,223 described thermally conductive elastomers comprising organopolysiloxanes, a particulate filler and a viscosity modifier.
La quantité de charge thermoconductrice dans les compositions silicones sont élevées, typiquement supérieure à 50% en poids, voire supérieure à 70% en poids. Une des difficultés de conception des silicones thermoconductrices réside dans l’ajout de si grandes quantités de charges thermoconductrices en minimisant l’impact sur la fluidité de la composition. Cela est particulièrement critique pour les compositions dites de « potting », dont la viscosité doit être faible, typiquement inférieure à The amount of thermally conductive filler in silicone compositions is high, typically greater than 50% by weight, or even greater than 70% by weight. One of the challenges in designing thermally conductive silicones lies in adding such large amounts of thermally conductive fillers while minimizing the impact on the fluidity of the composition. This is particularly critical for so-called “potting” compositions, whose viscosity must be low, typically less than
10 000 mPa.s, malgré une haute concentration en charges thermoconductrices. 10,000 mPa.s, despite a high concentration of thermally conductive fillers.
Plusieurs solutions ont été proposées dans l’art antérieur pour maîtriser la viscosité des compositions silicones thermoconductrices. Une méthode consiste à choisir attentivement le type de charge, sa forme et sa taille. Par exemple, la demande WO 2021/260279 Al de Elkem Silicones propose la sélections de certaines charges ayant des dimension spécifiques, avec un ratio à respecter entre grosses et petites particules. Le brevet EP 1 788 031 B1 de Shin-Etsu Chemical décrit un élastomère silicone thermoconducteur comprenant, pour 100 parts en poids d’une composition organopolysiloxane réticulable à chaud, de 10 à 2000 parts en poids d’une poudre de silicium métallique ayant une taille moyenne de particules inférieure à 100 pm. Une autre méthode consiste à changer le milieu de la formulation silicone ou d’ajouter un solvant. Toutefois, l’évaporation du solvant génère des composés volatils, liés à des risques pour l’hygiène et l’environnement. Enfin, une autre méthode consiste à traiter les charges thermoconductrices de façon à améliorer leur compatibilité avec la matrice silicone. Par exemple, la demande internationale de brevet WO 2023/283819 Al, déposée par Dow Silicones et Dow Global Technologies, décrit une composition silicone thermoconductrice autoadhésive comprenant notamment une charge thermoconductrice et un agent de traitement, en combinaison avec un agent promoteur d’adhésion contenant en même temps un atome d’hydrogène lié à un atome de silicium et au moins un groupe alcoxy lié à un atome de silicium. Cependant, l’ajout d’un agent de traitement dans la formulation peut avoir des impacts négatifs sur les propriétés mécaniques de l’élastomère silicone, et on note des phénomènes d’exsudation des agents de traitement hors de la matrice silicone. Several solutions have been proposed in the prior art to control the viscosity of thermally conductive silicone compositions. One method consists of carefully choosing the type of filler, its shape and its size. For example, application WO 2021/260279 A1 from Elkem Silicones proposes the selection of certain fillers having specific dimensions, with a ratio to be respected between large and small particles. Patent EP 1 788 031 B1 from Shin-Etsu Chemical describes a thermally conductive silicone elastomer comprising, per 100 parts by weight of a heat-crosslinkable organopolysiloxane composition, from 10 to 2000 parts by weight of a metallic silicon powder having an average particle size of less than 100 μm. Another method consists of changing the medium of the silicone formulation or adding a solvent. However, the evaporation of the solvent generates compounds volatile, linked to health and environmental risks. Finally, another method consists of treating the thermally conductive fillers so as to improve their compatibility with the silicone matrix. For example, international patent application WO 2023/283819 A1, filed by Dow Silicones and Dow Global Technologies, describes a self-adhesive thermally conductive silicone composition comprising in particular a thermally conductive filler and a treatment agent, in combination with an adhesion promoting agent containing at the same time a hydrogen atom bonded to a silicon atom and at least one alkoxy group bonded to a silicon atom. However, the addition of a treatment agent in the formulation can have negative impacts on the mechanical properties of the silicone elastomer, and phenomena of exudation of the treatment agents from the silicone matrix are noted.
L’objet de la présente invention est de proposer une nouvelle composition silicone thermoconductrice, résolvant les problèmes mentionnés ci-dessus, et possédant à la fois une haute teneur en charge thermoconductrice, une bonne conductivité thermique, et une faible viscosité. The object of the present invention is to provide a novel thermally conductive silicone composition, solving the problems mentioned above, and having both a high thermally conductive filler content, good thermal conductivity, and low viscosity.
Résumé de l’invention Summary of the invention
La présente invention a pour objet une composition silicone réticulable par réaction de polyaddition comprenant : The subject of the present invention is a silicone composition crosslinkable by polyaddition reaction comprising:
- au moins un organopolysiloxane A présentant, par molécule, au moins un groupe alcényle en C2-C12 lié au silicium, - at least one organopolysiloxane A having, per molecule, at least one C2-C12 alkenyl group linked to silicon,
- au moins un organopolysiloxane B présentant, par molécule, au moins deux motifs SiH, - at least one organopolysiloxane B having, per molecule, at least two SiH units,
- une quantité catalytiquement efficace d’au moins un catalyseur de polyaddition C, et - a catalytically effective amount of at least one polyaddition catalyst C, and
- une charge thermoconductrice D, caractérisée en ce que T organopolysiloxane A présente une viscosité à 25°C comprise entre 50 mPa.s et 200 mPa.s, et la teneur en motif siloxyle de type T est comprise entre 100 ppm et 1200 ppm. - a thermally conductive filler D, characterized in that organopolysiloxane A has a viscosity at 25°C of between 50 mPa.s and 200 mPa.s, and the content of siloxyl unit of type T is between 100 ppm and 1200 ppm.
Description détaillée de l’invention Detailed description of the invention
Sauf indication contraire, toutes les viscosités des huiles silicones dont il est question dans le présent exposé correspondent à une grandeur de viscosité dynamique à 25°C dite « Newtonienne », c’est-à- dire la viscosité dynamique qui est mesurée, de manière connue en soi, avec un viscosimètre Brookfield à un gradient de vitesse de cisaillement suffisamment faible pour que la viscosité mesurée soit indépendante du gradient de vitesse. Unless otherwise indicated, all viscosities of the silicone oils referred to in this disclosure correspond to a dynamic viscosity quantity at 25°C known as “Newtonian”, i.e. the dynamic viscosity which is measured, in a manner known per se, with a Brookfield viscometer at a shear rate gradient sufficiently low so that the measured viscosity is independent of the rate gradient.
Dans la partie qui suit concernant la description de T organopolysiloxane A, la nomenclature suivante a été utilisée pour représenter les motifs siloxyles : In the following section regarding the description of organopolysiloxane A, the following nomenclature has been used to represent the siloxyl units:
M : motif siloxyle R'sSiO , MV1 : motif siloxyle choisi parmi YRkSiOi/ et YzR'SiOi/z, de préférence YRkSiOi/ . M: siloxyl unit R'sSiO , M V1 : siloxyl unit chosen from YRkSiOi/ and YzR'SiOi/z, preferably YRkSiOi/ .
D : motif siloxyle R ’zS i O2/2, D: siloxyl unit R ’zS i O2/2,
DV1 : motif siloxyle choisi parmi YzSiCY/z et YR'SiCL/z, de préférence YR'SiCL/z, T : motif siloxyle R'SiOs/z, Q : motif siloxyle SiC>4/2, avec Y et R1 tels que : Y représente un groupe alcényle en C2-C12, de préférence un groupe vinyle ; R1 représente un groupe hydrocarboné monovalent ayant de 1 à 16 atomes de carbone, de préférence choisi parmi les groupes alkyles ayant de 1 à 8 atomes de carbone tels que les groupes méthyles, éthyles, propyles, les groupes cycloalkyles ayant de 3 à 8 atomes de carbone et les groupes aryles ayant de 6 à 12 atomes de carbone. D V1 : siloxyl unit chosen from YzSiCY/z and YR'SiCL/z, preferably YR'SiCL/z, T: siloxyl unit R'SiOs/z, Q: siloxyl unit SiC>4/2, with Y and R 1 such that: Y represents a C2-C12 alkenyl group, preferably a vinyl group; R 1 represents a monovalent hydrocarbon group having from 1 to 16 carbon atoms, preferably chosen from alkyl groups having from 1 to 8 carbon atoms such as methyl, ethyl, propyl groups, cycloalkyl groups having from 3 to 8 carbon atoms and aryl groups having from 6 to 12 carbon atoms.
A titre d’exemples de motifs terminaux M et MV1, on peut citer les groupes triméthylsiloxy, diméthylphénylsiloxy, diméthylvinylsiloxy ou diméthylhexènylsiloxy. Examples of terminal units M and M V1 include trimethylsiloxy, dimethylphenylsiloxy, dimethylvinylsiloxy or dimethylhexenylsiloxy groups.
A titre d’exemples de motifs D et DV1, on peut citer les groupes diméthylsiloxy, méthylphénylsiloxy, méthylvinylsiloxy, méthylbutènylsiloxy, méthylhexènylsiloxy, méthyldécènylsiloxy ou méthyldécadiènylsiloxy. Examples of D and D V1 units include dimethylsiloxy, methylphenylsiloxy, methylvinylsiloxy, methylbutenylsiloxy, methylhexenylsiloxy, methyldecenylsiloxy or methyldecadienylsiloxy groups.
A titre d’exemples de motifs T, on peut citer le groupe méthylsiloxy. Examples of T units include the methylsiloxy group.
L’organopoly siloxane A présentant, par molécule, au moins un groupe alcényle en C2-C12 lié au silicium, présente une structure essentiellement linéaire. Par “structure essentiellement linéaire”, on entend une structure dont la teneur en motifs siloxy T et/ou Q est inférieure ou égale à 2% (% massiques des motifs T et/ou Q, basés sur le poids total de l’organopoly siloxane A). Toutefois, l’organopolysiloxane A selon l’invention présente la caractéristique d’avoir une teneur en motif siloxyle de type T comprise entre 100 ppm et 1200 ppm, plus préférentiellement entre 200 ppm et 1000 ppm, et encore plus préférentiellement entre 300 ppm et 800 ppm. Dans le présent texte, la teneur en motif siloxyle de type T dans le composé organopolysiloxane A est une teneur massique, représentant le poids du motif T « S i O3/2 », par rapport au pour total du composé organopolysiloxane A. Elle peut être mesurée, de façon connue par l’homme du métier, par toute méthode de dosage appropriée. Elle peut alternativement être calculée de façon théorique en tenant compte de la masse de motifs T introduits dans le milieu réactionnel lors de la synthèse de l’organopolysiloxane A. Organopolysiloxane A having, per molecule, at least one C2-C12 alkenyl group bonded to silicon, has an essentially linear structure. By “essentially linear structure” is meant a structure whose content of siloxy units T and/or Q is less than or equal to 2% (% by mass of the units T and/or Q, based on the total weight of organopolysiloxane A). However, organopolysiloxane A according to the invention has the characteristic of having a content of siloxyl unit of type T of between 100 ppm and 1200 ppm, more preferably between 200 ppm and 1000 ppm, and even more preferably between 300 ppm and 800 ppm. In the present text, the content of T-type siloxyl unit in the organopolysiloxane compound A is a mass content, representing the weight of the T unit “S i O3/2”, relative to the total of the organopolysiloxane compound A. It can be measured, in a manner known to those skilled in the art, by any appropriate assay method. Alternatively, it can be calculated theoretically by taking into account the mass of T units introduced into the reaction medium during the synthesis of the organopolysiloxane A.
L’organopolysiloxane A peut présenter la formule moyenne générale suivante : [YR’zSiOi/zla [R SiOi/zlb [R1 2SiO2/2]c [R1SiO3/2]d dans laquelle Organopolysiloxane A can have the following general average formula: [YR'zSiOi/zla [R SiOi/zlb [R 1 2 SiO 2 /2]c [R 1 SiO 3/2 ]d in which
- Y représente un groupe alcényle en C2-C12, de préférence un groupe vinyle ; - Y represents a C2-C12 alkenyl group, preferably a vinyl group;
- R1 représente un groupe hydrocarboné monovalent ayant de 1 à 16 atomes de carbone, de préférence choisi parmi les groupes alkyles ayant de 1 à 8 atomes de carbone tels que les groupes méthyle, éthyle, propyle, les groupes cycloalkyles ayant de 3 à 8 atomes de carbone et les groupes aryle ayant de 6 à 12 atomes de carbone ; et - a, b, c et d sont tels que a > 0, b > 0, a+b =2, c > 1, d > 0, de préférence c est compris entre 1 et 200, et la concentration massique en motif siloxyle de type T est comprise entre 100 ppm et 1200 ppm.- R 1 represents a monovalent hydrocarbon group having from 1 to 16 carbon atoms, preferably chosen from alkyl groups having from 1 to 8 carbon atoms such as methyl, ethyl, propyl groups, cycloalkyl groups having from 3 to 8 carbon atoms and aryl groups having from 6 to 12 carbon atoms; and - a, b, c and d are such that a > 0, b > 0, a+b =2, c > 1, d > 0, preferably c is between 1 and 200, and the mass concentration of T-type siloxyl unit is between 100 ppm and 1200 ppm.
Il est entendu dans les formules ci-dessus que, si plusieurs groupes R1 sont présents, ils peuvent être identiques ou différents les uns des autres. It is understood in the above formulas that if more than one R 1 group is present, they may be the same or different from each other.
Selon un mode de réalisation préféré, bien que cela ne soit pas représenté sur la formule générale, l’organopolysiloxane A peut contenir des groupements hydroxy OH portés par des motifs siloxy en bout de chaine et/ou en milieu de chaine. L’organopolysiloxane A peut contenir de préférence entre 130 ppm et 1000 ppm de groupes OH liés au silicium, plus préférentiellement entre 150 ppm et 900 ppm. La teneur en groupes OH liés au silicium dans le composé organopolysiloxane A est une teneur massique (poids OH/poids échantillon). Elle peut être mesurée par une méthode infrarouge après deutération telle que décrite dans “Measurement of Trace Silanol in Siloxanes by IR Spectroscopy” par Elmer D. Lipp, Applied Spectroscopy vol. 45, no. 3, 1991, pp. 477-483. Pour ce faire, un échantillon est analysé grâce à un spectrophotomètre IRTF (infrarouge à transformée de Fourier). According to a preferred embodiment, although not shown in the general formula, organopolysiloxane A may contain hydroxy OH groups carried by siloxy units at the end of the chain and/or in the middle of the chain. Organopolysiloxane A may preferably contain between 130 ppm and 1000 ppm of OH groups bonded to silicon, more preferably between 150 ppm and 900 ppm. The content of OH groups bonded to silicon in organopolysiloxane compound A is a mass content (OH weight/sample weight). It can be measured by an infrared method after deuteration as described in “Measurement of Trace Silanol in Siloxanes by IR Spectroscopy” by Elmer D. Lipp, Applied Spectroscopy vol. 45, no. 3, 1991, pp. 477-483. To do this, a sample is analyzed using an IRTF (Fourier transform infrared) spectrophotometer.
Les groupements hydroxy OH portés par des motifs siloxy en bout de chaine peuvent être représentés par la formule R'2(OH)SiOi/2, et les groupements hydroxy OH portés par des motifs siloxy en milieu de chaine peuvent être représentés par la formule R1(OH)SiO2/2-The hydroxy OH groups carried by siloxy units at the end of the chain can be represented by the formula R'2(OH)SiOi/2, and the hydroxy OH groups carried by siloxy units in the middle of the chain can be represented by the formula R 1 (OH)SiO2/2-
De préférence, le composé organopolysiloxane A a une teneur massique en motif alcényle comprise entre 0,01% et 10%, de préférence entre 0,1% et 5% (% massiques des motifs alcényles, basés sur le poids total de l’organopolysiloxane A). Preferably, the organopolysiloxane compound A has a mass content of alkenyl units of between 0.01% and 10%, preferably between 0.1% and 5% (mass % of alkenyl units, based on the total weight of the organopolysiloxane A).
Lesdits organopolysiloxanes A sont des huiles de viscosité dynamique comprise entre 50 mPa.s et 200 mPa.s, de préférence entre 80 mPa.s et 150 mPa.s, de manière plus préférée entre 100 mPa.s et 130 mPa.s. La viscosité dynamique est mesurée à 25°C de manière connue en soi, avec un viscosimètre Brookfield à un gradient de vitesse de cisaillement suffisamment faible pour que la viscosité mesurée soit indépendante du gradient de vitesse. Said organopolysiloxanes A are oils with a dynamic viscosity of between 50 mPa.s and 200 mPa.s, preferably between 80 mPa.s and 150 mPa.s, more preferably between 100 mPa.s and 130 mPa.s. The dynamic viscosity is measured at 25°C in a manner known per se, with a Brookfield viscometer at a shear rate gradient sufficiently low so that the measured viscosity is independent of the rate gradient.
Selon un mode de réalisation, l’organopolysiloxane A peut présenter une teneur en acidité résiduelle. La teneur en acidité résiduelle peut être supérieure ou égale à 5 ppm, de manière préférée comprise entre 6 ppm et 100 ppm, et de manière plus préféré comprise entre 10 ppm et 100 ppm. La présence d’une acidité résiduelle supérieure ou égale à 5 ppm, de manière préférée comprise entre 6 ppm et 100 ppm, dans l’organopolysiloxane A pourrait permettre de diminuer la viscosité la composition silicone réticulable par réaction de polyaddition selon la présente invention et d’améliorer son indice de thixotropic. According to one embodiment, the organopolysiloxane A may have a residual acidity content. The residual acidity content may be greater than or equal to 5 ppm, preferably between 6 ppm and 100 ppm, and more preferably between 10 ppm and 100 ppm. The presence of a residual acidity greater than or equal to 5 ppm, preferably between 6 ppm and 100 ppm, in the organopolysiloxane A could make it possible to reduce the viscosity of the silicone composition crosslinkable by polyaddition reaction according to the present invention and to improve its thixotropic index.
Selon un autre mode de réalisation, l’organopolysiloxane A ne présente pas, ou pas significativement, d’acidité résiduelle. La teneur en acidité résiduelle peut être strictement inférieure à 5 ppm, de manière préférée inférieure à 4 ppm, et de manière plus préférée inférieure à 3 ppm. Sans vouloir être lié par cette théorie, les inventeurs pensent que l’absence d’acidité résiduelle significative dans l’organopolysiloxane A a pour avantage d’améliorer la stabilité dans le temps dudit organopolysiloxane, notamment à haute température. De ce fait, la composition silicone réticulable par réaction de polyaddition selon la présente invention peut présenter une meilleure stabilité dans le temps et une durée limite de stockage plus longue. According to another embodiment, organopolysiloxane A does not have, or does not significantly have, residual acidity. The residual acidity content may be strictly less than 5 ppm, preferably less than 4 ppm, and more preferably less than 3 ppm. Without wishing to be bound by this theory, the inventors believe that the absence of significant residual acidity in organopolysiloxane A has the advantage of improving the stability over time of said organopolysiloxane, in particular at high temperature. As a result, the silicone composition crosslinkable by polyaddition reaction according to the present invention can have better stability over time and a longer storage life.
Dans le présent texte, l’acidité est exprimée en ppm massique équivalent HCl (acide chlorhydrique), i.e. mg/kg d’équivalents d’HCl. La mesure de la teneur en acidité peut être faite à l’aide d’un spectrophotomètre UV-visible, par mesure de la différence de transmittance entre l’échantillon analysé et un étalon obtenu par ajouts dosés connus d’HCl. In this text, acidity is expressed in ppm mass equivalent HCl (hydrochloric acid), i.e. mg/kg of HCl equivalents. The measurement of the acidity content can be made using a UV-visible spectrophotometer, by measuring the difference in transmittance between the sample analyzed and a standard obtained by known dosed additions of HCl.
L’organopolysiloxane A selon l’invention peut être sélectionné parmi les composés disponibles dans le commerce respectant les spécifications énoncées. Alternativement, il pourra être synthétisé selon les méthodes connues du domaine technique. The organopolysiloxane A according to the invention can be selected from commercially available compounds meeting the stated specifications. Alternatively, it can be synthesized according to methods known in the technical field.
Selon un mode de réalisation, l’organopolysiloxane A est obtenu par polymérisation par ouverture de cycles (ou ROP pour ring-opening polymerization) en présence d’initiateurs nucléophiles ou électrophiles. Ces méthodes de synthèses sont bien connues de l’homme du métier et sont par exemple décrites dans l’article « Ring-Opening Polymerization (ROP) and Catalytic Rearrangement as a Way to Obtain Siloxane Mono- and Telechelics, as Well as Well-Organized Branching Centers : History and Prospects », Bezlepkina et al, Polymers 2022, 14, 2408. Ces méthodes permettent de contrôler efficacement le poids moléculaire du polymère grâce à la sélection de la quantité d’initiateur et à la quantité de bloqueurs de chaînes. La synthèse d’ organopolysiloxane A selon la présente invention peut être réalisée par une polymérisation anionique ou par une polymérisation cationique. Pour une polymérisation anionique, l’initiateur pourra être choisi parmi les catalyseurs nucléophiles bien connus de l’homme du métier. Pour une polymérisation cationique, l’initiateur pourra être choisi parmi les catalyseurs acides bien connus de l’homme du métier. According to one embodiment, organopolysiloxane A is obtained by ring-opening polymerization (ROP) in the presence of nucleophilic or electrophilic initiators. These synthesis methods are well known to those skilled in the art and are for example described in the article “Ring-Opening Polymerization (ROP) and Catalytic Rearrangement as a Way to Obtain Siloxane Mono- and Telechelics, as Well as Well-Organized Branching Centers: History and Prospects”, Bezlepkina et al, Polymers 2022, 14, 2408. These methods make it possible to effectively control the molecular weight of the polymer by selecting the amount of initiator and the amount of chain blockers. The synthesis of organopolysiloxane A according to the present invention can be carried out by anionic polymerization or by cationic polymerization. For anionic polymerization, the initiator may be chosen from nucleophilic catalysts well known to those skilled in the art. For cationic polymerization, the initiator may be chosen from acid catalysts well known to those skilled in the art.
L’utilisation de bloqueurs de chaînes contenant des fonctions alcényles (de préférence vinyles) permet de synthétiser des organopolysiloxanes possédant des groupes alcényles (de préférence vinyles) en positions terminales. La synthèse d’ organopolysiloxane A selon la présente invention pourra donc être réalisée à partir d’oligosiloxanes cycliques, typiquement l’hexaméthylcyclotrisiloxane (D3) ou l’octaméthylcyclotétrasiloxane (D4), et de bloqueurs de chaînes alcénylés, de préférence vinylés, typiquement le divinyldiméthyldisiloxane (MV12). The use of chain blockers containing alkenyl (preferably vinyl) functions makes it possible to synthesize organopolysiloxanes having alkenyl (preferably vinyl) groups in terminal positions. The synthesis of organopolysiloxane A according to the present invention can therefore be carried out from cyclic oligosiloxanes, typically hexamethylcyclotrisiloxane (D3) or octamethylcyclotetrasiloxane (D4), and alkenyl, preferably vinyl, chain blockers, typically divinyldimethyldisiloxane (M V1 2).
La teneur en motif siloxyle Si-Os/2 de type T peut être contrôlée par ajout d’une source de motif siloxyle de type T lors de la synthèse. Cette source de motif siloxyle de type T peut être choisie parmi un organopolysiloxane branché contenant des motifs siloxyles de type T un composé silane portant au moins un motif T. Selon un premier mode de réalisation, la source de motif siloxyle de type T est un organopolysiloxane branchée par contenant des motifs siloxyles de type T, de préférence une résine silicone ayant un faible poids moléculaire et/ou de faible viscosité. Selon un second mode de réalisation, la source de motif siloxyle de type T est un composé silane portant au moins un le motif T, de préférence un composé silane de formule R3Si(OR4)s, dans laquelle R3 représente un groupe hydrocarboné monovalent ayant de 1 à 16 atomes de carbone, de préférence choisi parmi les groupes alkyles ayant de 1 à 8 atomes de carbone tels que les groupes méthyles, éthyles, propyles, les groupes cycloalkyles ayant de 3 à 8 atomes de carbone et les groupes aryles ayant de 6 à 12 atomes de carbone ; et chaque R4 représente, indépendamment les uns des autres, un groupe hydrocarboné monovalent ayant de 1 à 16 atomes de carbone, de préférence choisi parmi les groupes alkyles ayant de 1 à 8 atomes de carbone tels que les groupes méthyles, éthyles, propyles, les groupes cycloalkyles ayant de 3 à 8 atomes de carbone et les groupes aryles ayant de 6 à 12 atomes de carbone, les groupes alcényles en C2-C1, tels que le groupe vinyle, et les groupes -Si(R5)3, dans lesquels chaque R5 représente, indépendamment les uns des autres, un groupe hydrocarboné monovalent ayant de 1 à 16 atomes de carbone, de préférence choisi parmi les groupes alkyles ayant de 1 à 8 atomes de carbone tels que les groupes méthyles, éthyles, propyles, les groupes cycloalkyles ayant de 3 à 8 atomes de carbone et les groupes aryles ayant de 6 à 12 atomes de carbone, les groupes alcényles en C2-C1, tels que le groupe vinyle. De préférence, selon ledit second mode de réalisation, la source de motif siloxyle de type T est un composé silane portant au moins un le motif T, de préférence un composé silane de formule R3Si(OR4)s, dans laquelle R3 représente un groupe hydrocarboné monovalent ayant de 1 à 16 atomes de carbone; et chaque R4 représente, indépendamment les uns des autres, un groupe hydrocarboné monovalent ayant de 1 à 16 atomes de carbone. The content of T-type Si-Os/2 siloxyl unit can be controlled by adding a source of T-type siloxyl unit during synthesis. This source of T-type siloxyl unit can be chosen from a branched organopolysiloxane containing T-type siloxyl units or a silane compound carrying at least one T-unit. According to a first embodiment, the source of T-type siloxyl unit is a branched organopolysiloxane containing T-type siloxyl units, preferably a silicone resin having a low molecular weight and/or low viscosity. According to a second embodiment, the source of T-type siloxyl unit is a silane compound carrying at least one T-unit, preferably a silane compound of formula R 3 Si(OR 4 )s, in which R 3 represents a group monovalent hydrocarbon having from 1 to 16 carbon atoms, preferably chosen from alkyl groups having from 1 to 8 carbon atoms such as methyl, ethyl, propyl groups, cycloalkyl groups having from 3 to 8 carbon atoms and aryl groups having from 6 to 12 carbon atoms; and each R 4 represents, independently of one another, a monovalent hydrocarbon group having from 1 to 16 carbon atoms, preferably selected from alkyl groups having from 1 to 8 carbon atoms such as methyl, ethyl, propyl groups, cycloalkyl groups having from 3 to 8 carbon atoms and aryl groups having from 6 to 12 carbon atoms, C2-C1 alkenyl groups, such as the vinyl group, and -Si(R 5 )3 groups, in which each R 5 represents, independently of one another, a monovalent hydrocarbon group having from 1 to 16 carbon atoms, preferably selected from alkyl groups having from 1 to 8 carbon atoms such as methyl, ethyl, propyl groups, cycloalkyl groups having from 3 to 8 carbon atoms and aryl groups having from 6 to 12 carbon atoms, the groups C2-C1 alkenyls, such as the vinyl group. Preferably, according to said second embodiment, the source of T-type siloxyl unit is a silane compound carrying at least one of the T unit, preferably a silane compound of formula R 3 Si(OR 4 )s, in which R 3 represents a monovalent hydrocarbon group having from 1 to 16 carbon atoms; and each R 4 represents, independently of each other, a monovalent hydrocarbon group having from 1 to 16 carbon atoms.
Selon un mode de réalisation préféré, lorsque l’organopoly siloxane A contient des groupements hydroxy OH liés au silicium, la teneur en groupes OH liés au silicium peut être contrôlée par ajout d’une source de groupes OH lors de la synthèse. Cette source de groupes OH peut être choisie parmi : un oligo-organosiloxane a,co-dihydroxylé, un polyorganosiloxane a,co-dihydroxylé, du Silox, une résine silicone hydroxylée, ou de l’eau. Lesdits oligo- et polyorganosiloxanes a,co-dihydroxylés sont choisi de préférence parmi ceux ayant un faible poids moléculaire, de préférence inférieur à 20000 g/mol, plus préférentiellement inférieur à 15000 g/mol (masse molaire moyenne en poids), et/ou de faible viscosité, de préférence inférieure à 1000 mPa.s. Par « Silox », on entend des mélanges d’ oligo- ou polyorganosiloxane a,co-dihydroxylé et de cyclosiloxanes. Ces mélanges sont issus de la synthèse directe des organochlorosilanes (synthèse de Rochow) et de l’hydrolyse des chlorosilanes obtenus. According to a preferred embodiment, when the organopoly siloxane A contains silicon-bonded hydroxy OH groups, the content of silicon-bonded OH groups can be controlled by adding a source of OH groups during the synthesis. This source of OH groups can be chosen from: an α,β-dihydroxylated oligo-organosiloxane, an α,β-dihydroxylated polyorganosiloxane, Silox, a hydroxylated silicone resin, or water. Said α,β-dihydroxylated oligo- and polyorganosiloxanes are preferably chosen from those having a low molecular weight, preferably less than 20,000 g/mol, more preferably less than 15,000 g/mol (weight-average molar mass), and/or low viscosity, preferably less than 1,000 mPa.s. The term "Silox" refers to mixtures of α,β-dihydroxylated oligo- or polyorganosiloxane and cyclosiloxanes. These mixtures are obtained from the direct synthesis of organochlorosilanes (Rochow synthesis) and the hydrolysis of the resulting chlorosilanes.
La composition silicone comprend de préférence de 5% à 50% en poids d’organopolysiloxane A, encore plus préférentiellement de 10% à 40% en poids d’organopolysiloxane A. The silicone composition preferably comprises from 5% to 50% by weight of organopolysiloxane A, even more preferably from 10% to 40% by weight of organopolysiloxane A.
Dans la partie qui suit concernant la description de l’organopoly siloxane B, la nomenclature suivante a été utilisée pour représenter les motifs siloxyles : M : motif siloxyle R23SiOi/2, M’ : motif siloxyle R22HSiOi/2, D : motif siloxyle R22SiC>2/2, D’ : motif siloxyle R2HsiC>2/2, T : motif siloxyle R2SiC>3/2, In the following section concerning the description of organopolysiloxane B, the following nomenclature has been used to represent the siloxyl units: M: siloxyl unit R 2 3SiOi/2, M': siloxyl unit R 2 2HSiOi/2, D: siloxyl unit R 2 2SiC>2/2, D': siloxyl unit R 2 HsiC>2/2, T: siloxyl unit R 2 SiC>3/2,
Q : motif siloxyle SiC>4/2, avec R2 représentant un radical monovalent ayant de 1 à 12 atomes de carbone. Q: siloxyl unit SiC>4/2, with R 2 representing a monovalent radical having from 1 to 12 carbon atoms.
L’organopoly siloxane B est un organopolysiloxane présentant, par molécule, au moins deux motifs SiH. Il s’agit donc d’un composé organohydrogénopoly siloxane. De préférence, l’ organopolysiloxane B comprend au moins trois motifs SiH. Organopolysiloxane B is an organopolysiloxane having, per molecule, at least two SiH units. It is therefore an organohydrogenopolysiloxane compound. Preferably, organopolysiloxane B comprises at least three SiH units.
L’ organopolysiloxane B peut avantageusement être un organopolysiloxane comprenant au moins deux, de préférence au moins trois, motifs siloxyles de formule suivante : HdR2 eSiO<4 d e)/2 dans laquelle R2 représente un radical monovalent ayant de 1 à 12 atomes de carbone, d = 1 ou 2, e = 0, 1 ou 2 et d+e = 1 , 2 ou 3 ; et éventuellement d’autres motifs de formule suivante : R2fSiO<4 f)/2 dans laquelle R2 a la même signification que ci-dessus, et f = 0, 1, 2, ou 3. The organopolysiloxane B may advantageously be an organopolysiloxane comprising at least two, preferably at least three, siloxyl units of the following formula: HdR 2 e SiO<4 de)/2 in which R 2 represents a monovalent radical having from 1 to 12 carbon atoms, d = 1 or 2, e = 0, 1 or 2 and d+e = 1, 2 or 3; and optionally other units of the following formula: R 2 fSiO<4 f)/2 in which R 2 has the same meaning as above, and f = 0, 1, 2, or 3.
Il est entendu que, si plusieurs groupes R2 sont présents dans les formules ci-dessus, ils peuvent être identiques ou différents les uns des autres. It is understood that if several R 2 groups are present in the above formulas, they may be the same or different from each other.
Préférentiellement, R2 peut représenter un radical monovalent choisi dans le groupe constitué par les groupes alkyles ayant 1 à 8 atomes de carbone, éventuellement substitué par au moins un atome d’halogène tel que le chlore ou le fluor, les groupes cycloalkyles ayant de 3 à 8 atomes de carbone et les groupes aryles ayant de 6 à 12 atomes de carbone. R2 peut avantageusement être choisi dans le groupe constitué par le méthyle, l’éthyle, le propyle, le 3,3,3-trifluoropropyle, le xylyle, le tolyle et le phényle. Preferably, R 2 may represent a monovalent radical chosen from the group consisting of alkyl groups having 1 to 8 carbon atoms, optionally substituted by at least one halogen atom such as chlorine or fluorine, cycloalkyl groups having from 3 to 8 carbon atoms and aryl groups having from 6 to 12 carbon atoms. R 2 may advantageously be chosen from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl.
Le symbole d est préférentiellement égal à 1. The symbol d is preferably equal to 1.
L’ organopolysiloxane B peut présenter une structure linéaire, ramifiée, ou cyclique. Le degré de polymérisation est de préférence supérieur ou égal à 2. Généralement, il est inférieur à 5000. De préférence, la viscosité de l’ organopolysiloxane B est comprise entre 1 mPa.s et 5000 mPa.s, plus préférentiellement entre 1 mPa.s et 2000 mPa.s, et encore plus préférentiellement entre 5 mPa.s et 1000 mPa.s. Organopolysiloxane B may have a linear, branched, or cyclic structure. The degree of polymerization is preferably greater than or equal to 2. Generally, it is less than 5000. Preferably, the viscosity of organopolysiloxane B is between 1 mPa.s and 5000 mPa.s, more preferably between 1 mPa.s and 2000 mPa.s, and even more preferably between 5 mPa.s and 1000 mPa.s.
Lorsqu’il s’agit de polymères linéaires, ceux-ci sont essentiellement constitués de motifs siloxyles D et/ou D’, et de motifs siloxyles terminaux M et/ou M’. Lorsqu’il s’agit de polymères cycliques, ceux- ci sont essentiellement constitué de motifs siloxyles D et/ou D’. Des exemples d’organohydrogénopolysiloxanes pouvant être des organopolysiloxanes B selon l’invention sont :When linear polymers are concerned, these are essentially constituted of siloxyl units D and/or D', and of terminal siloxyl units M and/or M'. When cyclic polymers are concerned, these are essentially constituted of siloxyl units D and/or D'. Examples of organohydrogenpolysiloxanes which may be organopolysiloxanes B according to the invention are:
- un poly(diméthylsiloxane) à extrémités hydrogénodiméthylsilyles ; - a poly(dimethylsiloxane) with hydrogenodimethylsilyl ends;
- un poly(diméthylsiloxane-co-méthylhydrogénosiloxane) à extrémités triméthylsilyles ; - a poly(dimethylsiloxane-co-methylhydrogensiloxane) with trimethylsilyl ends;
- un poly(diméthylsiloxane-co-méthylhydrogénosiloxane) à extrémités hydrogénodiméthylsilyles ;- a poly(dimethylsiloxane-co-methylhydrogensiloxane) with hydrogenodimethylsilyl ends;
- un poly(méthylhydrogénosiloxane) à extrémités triméthyisilyles ; et - a poly(methylhydrogensiloxane) with trimethylsilyl ends; and
- un poly(méthylhydrogénosiloxane) cyclique. Lorsque organopolysiloxane B présente une structure ramifiée, il est choisi de préférence dans le groupe constitué par les résines silicones de formules suivantes : - a cyclic poly(methylhydrogensiloxane). When organopolysiloxane B has a branched structure, it is preferably chosen from the group consisting of silicone resins of the following formulae:
- M’Q où les atomes d’hydrogène liés à des atomes de silicium sont portés par les groupes M ; - M’Q where the hydrogen atoms linked to silicon atoms are carried by the M groups;
- MM’Q où les atomes d’hydrogène liés à des atomes de silicium sont portés par une partie des motifs M ; - MM’Q where the hydrogen atoms linked to silicon atoms are carried by part of the M motifs;
- MD’Q où les atomes d’hydrogène liés à des atomes de silicium sont portés par les groupes D ; - MD’Q where the hydrogen atoms linked to silicon atoms are carried by the D groups;
- MDD’Q où les atomes d’hydrogène liés à des atomes de silicium sont portés par une partie des groupes D ; - MDD’Q where the hydrogen atoms linked to silicon atoms are carried by part of the D groups;
- MM’TQ où les atomes d’hydrogène liés à des atomes de silicium sont portés par une partie des motifs M ; - MM’TQ where the hydrogen atoms linked to silicon atoms are carried by part of the M motifs;
- MM’DD’Q où les atomes d’hydrogène liés à des atomes de silicium sont portés par une partie des motifs M et D ; - MM’DD’Q where the hydrogen atoms linked to silicon atoms are carried by part of the M and D motifs;
- et leurs mélanges. - and their mixtures.
De préférence, l’ organopolysiloxane B a une teneur massique en fonctions hydrogénosilyle Si-H comprise entre 0,2% et 91% plus préférentiellement entre 3% et 80% et encore plus préférentiellement entre 15% et 70%. Preferably, the organopolysiloxane B has a mass content of hydrogenosilyl Si-H functions of between 0.2% and 91%, more preferably between 3% and 80% and even more preferably between 15% and 70%.
La composition silicone selon l’invention comprend de préférence 0,1% à 15% en poids, et plus préférentiellement de 0,5% à 10% en poids, d’organopolysiloxane B. La composition silicone selon l’invention peut comprendre un organopolysiloxane B ou un mélanges de plusieurs organopolysiloxanes B, par exemple un mélange d’un poly(diméthylsiloxane) à extrémités hydrogénodiméthylsilyles et de organopolysiloxane présentant, par molécule, au moins trois motifs SiH. The silicone composition according to the invention preferably comprises 0.1% to 15% by weight, and more preferably from 0.5% to 10% by weight, of organopolysiloxane B. The silicone composition according to the invention may comprise an organopolysiloxane B or a mixture of several organopolysiloxanes B, for example a mixture of a poly(dimethylsiloxane) with hydrogenodimethylsilyl ends and of organopolysiloxane having, per molecule, at least three SiH units.
Avantageusement, le ratio molaire des fonctions hydrogénosilyles Si-H des organopolysiloxanes B sur les fonctions alcènes des organopolysiloxanes A est compris entre 0,2 et 10, de préférence entre 0,5 et 5. Advantageously, the molar ratio of the hydrogenosilyl functions Si-H of the organopolysiloxanes B to the alkene functions of the organopolysiloxanes A is between 0.2 and 10, preferably between 0.5 and 5.
Le catalyseur de polyaddition C peut notamment être choisi parmi les composés du platine et du rhodium mais aussi parmi des composés de silicium comme ceux décrits dans les demandes de brevet WO 2015/004396 et WO 2015/004397, des composés de germanium comme ceux décrits dans la demande de brevet WO 2016/075414, des complexes de nickel, cobalt ou fer comme ceux décrits dans les demandes de brevet WO 2016/071651, WO 2016/071652, WO 2016/071654, WO 2018/115601, WO 2019/008279, WO 2019/138194, WO 2023/031524 et WO 2023/031525, ou des complexes de manganèse comme ceux décrits dans les demandes WO 2023/139322 et WO 2024/146993. Le catalyseur C est de préférence un composé dérivé d’au moins un métal appartenant au groupe du platine. Ces catalyseurs sont bien connus. On peut, en particulier, utiliser les complexes du platine et d’un produit organique décrit dans les brevets US 3,159,601, US 3,159,602, US 3,220,972 et les brevets européens EP 0.057.459, EP 0.188.978 et EP 0.190.530, les complexes du platine et d’organosiloxanes vinylés décrits dans les brevets US 3,419,593, US 3,715,334, US 3,377,432 et US 3,814,730. The polyaddition catalyst C may in particular be chosen from platinum and rhodium compounds but also from silicon compounds such as those described in patent applications WO 2015/004396 and WO 2015/004397, germanium compounds such as those described in patent application WO 2016/075414, nickel, cobalt or iron complexes such as those described in patent applications WO 2016/071651, WO 2016/071652, WO 2016/071654, WO 2018/115601, WO 2019/008279, WO 2019/138194, WO 2023/031524 and WO 2023/031525, or manganese complexes such as those described in applications WO 2023/139322 and WO 2024/146993. Catalyst C is preferably a compound derived from at least one metal belonging to the platinum group. These catalysts are well known. In particular, it is possible to use the complexes of platinum and an organic product described in US patents 3,159,601, US 3,159,602, US 3,220,972 and European patents EP 0.057.459, EP 0.188.978 and EP 0.190.530, the complexes of platinum and of vinyl organosiloxanes described in US patents 3,419,593, US 3,715,334, US 3,377,432 and US 3,814,730.
Alternativement, un photocatalyseur de polyaddition peut être utilisé. Un tel catalyseur peut être activé par irradiation, de préférence par irradiation UV. Un photocatalyseur à base de platine peut être choisi par exemple parmi : le bis(acétylacétonate) de platine, le triméthyl(acétylacétonate) de platine, le triméthyl(2,4-pentanedione) de platine, le triméthyl(3 ,5 -heptanedione) de platine, le triméthyl(méthyl acétoacétate) de platine, le bis(2,4-pentanedione) de platine, le bis(2,4-hexanedione) de platine, le bis(2,4-heptanedione) de platine, le bis(3,5-heptanedione) de platine et le bis(l-phényl-l,3- butanedione) de platine. Alternatively, a polyaddition photocatalyst may be used. Such a catalyst may be activated by irradiation, preferably by UV irradiation. A platinum-based photocatalyst may be selected, for example, from: platinum bis(acetylacetonate), platinum trimethyl(acetylacetonate), platinum trimethyl(2,4-pentanedione), platinum trimethyl(3,5-heptanedione), platinum trimethyl(methyl acetoacetate), platinum bis(2,4-pentanedione), platinum bis(2,4-hexanedione), platinum bis(2,4-heptanedione), platinum bis(3,5-heptanedione) and platinum bis(1-phenyl-1,3-butanedione).
Préférentiellement, le catalyseur C est un composé dérivé du platine. Dans ce cas, la quantité pondérale de catalyseur C, calculée en poids de platine-métal, est généralement comprise entre 2 ppm et 400 ppm massiques, de préférence entre 5 ppm et 200 ppm, basée sur le poids total de la composition silicone. Preferably, catalyst C is a compound derived from platinum. In this case, the weight quantity of catalyst C, calculated as the weight of platinum metal, is generally between 2 ppm and 400 ppm by mass, preferably between 5 ppm and 200 ppm, based on the total weight of the silicone composition.
Préférentiellement, le catalyseur C est un platine de Karstedt. Preferably, catalyst C is a Karstedt platinum.
La composition silicone réticulable par réaction de polyaddition selon la présente invention se caractérise notamment par le fait qu’elle comprend une charge thermoconductrice D. Celle-ci peut être constituée d’une seule charge ou d’un mélange de charges ayant une nature chimique différente et/ou une structure différente et/ou une granulométrie différente. Selon un mode de réalisation de la présente invention, la charge thermoconductrice D est constituée d’un mélange d’au moins deux charges ou d’au moins trois charges ayant une nature chimique et/ou une granulométrie différente. Selon un autre mode de réalisation de la présente invention, la charge thermoconductrice D est constituée d’une seule charge. The silicone composition crosslinkable by polyaddition reaction according to the present invention is characterized in particular by the fact that it comprises a thermally conductive filler D. This may consist of a single filler or a mixture of fillers having a different chemical nature and/or a different structure and/or a different particle size. According to one embodiment of the present invention, the thermally conductive filler D consists of a mixture of at least two fillers or at least three fillers having a different chemical nature and/or a different particle size. According to another embodiment of the present invention, the thermally conductive filler D consists of a single filler.
Le poids total de la charge thermoconductrice D dans la composition silicone réticulable par réaction de polyaddition est de préférence supérieur à 50%, de façon plus préférée supérieur à 60%, et de façon encore plus préférée compris entre 70% et 95%, en poids par rapport au poids total de la composition silicone réticulable par réaction de polyaddition. The total weight of the thermally conductive filler D in the silicone composition crosslinkable by polyaddition reaction is preferably greater than 50%, more preferably greater than 60%, and even more preferably between 70% and 95%, by weight relative to the total weight of the silicone composition crosslinkable by polyaddition reaction.
La charge thermoconductrice D peut contenir une ou plusieurs charges de nature différente connues par l’homme du métier pour ses propriétés thermoconductrices, notamment parmi les métaux, les alliages, les oxydes métalliques, les hydroxydes métalliques, les nitrures métalliques, les carbures métalliques, les siliciures métalliques, le carbone, les alliages magnétiques doux et les ferrites. La conductivité thermique de ces charges est de préférence supérieure à 10 W/m.K, de façon plus préférée supérieure à 20 W/m.K, et de façon encore plus préférée supérieure à 50 W/m.K. Elles pourront notamment être choisies dans le groupe constitué par l’alumine, le trihydrate d’aluminium (ATH), l’aluminium, la silice, le silicium métallique, le carbure de silicium, le nitrure de silicium, l’oxyde de magnésium, le carbonate de magnésium, le nitrure de bore, l’oxyde de zinc, le nitrure d’aluminium, et le carbone, par exemple noir de carbone, diamant, nanotubes de carbone, graphite et graphène. De préférence, la charge thermoconductrice D peut comprendre une charge thermoconductrice choisie dans le groupe constitué par une charge d’alumine, une charge de trihydrate d’aluminium (ATH), une charge d’aluminium, une charge de silice, une charge de silicium métallique une charge d’oxyde de zinc, une charge de nitrure d’aluminium, une charge de nitrure de bore, et leurs mélanges. De façon encore plus préférée, la charge thermoconductrice D peut comprendre une charge thermoconductrice choisie dans le groupe constitué par une charge d’alumine, une charge de trihydrate d’aluminium (ATH), une charge d’oxyde de zinc, une charge de silice, et leurs mélanges. The thermally conductive filler D may contain one or more fillers of different nature known to those skilled in the art for their thermally conductive properties, in particular among metals, alloys, metal oxides, metal hydroxides, metal nitrides, metal carbides, metal silicides, carbon, soft magnetic alloys and ferrites. The thermal conductivity of these fillers is preferably greater than 10 W/mK, more preferably greater than 20 W/mK, and even more preferably greater than 50 W/mK. They may in particular be chosen from the group consisting of alumina, aluminum trihydrate (ATH), aluminum, silica, metallic silicon, silicon carbide, silicon nitride, magnesium oxide, magnesium carbonate, boron nitride, zinc oxide, aluminum nitride, and carbon, for example carbon black, diamond, carbon nanotubes, graphite and graphene. Preferably, the thermally conductive filler D may comprise a thermally conductive filler selected from the group consisting of an alumina filler, an aluminum trihydrate (ATH) filler, an aluminum filler, a silica filler, a metallic silicon filler, a zinc oxide filler, an aluminum nitride filler, a boron nitride filler, and mixtures thereof. Even more preferably, the thermally conductive filler D may comprise a thermally conductive filler selected from the group consisting of an alumina filler, an aluminum trihydrate (ATH) filler, a zinc oxide filler, a silica filler, and mixtures thereof.
La charge thermoconductrice D peut avoir n’importe quelle forme connue de l’homme du métier, par exemple une forme sphérique, une forme en aiguille, une forme de disque, une forme de bâtonnet, ou bien une forme indéfinie. De préférence, la charge thermoconductrice à une forme sphérique ou une forme indéfinie. Lorsque différentes charges thermoconductrices sont utilisées en mélanges, celles-ci peuvent avoir la même forme ou des formes différentes. The thermally conductive filler D may have any shape known to those skilled in the art, for example a spherical shape, a needle shape, a disc shape, a rod shape, or an indefinite shape. Preferably, the thermally conductive filler has a spherical shape or an indefinite shape. When different thermally conductive fillers are used in mixtures, these may have the same shape or different shapes.
La ou les charges thermoconductrices peuvent être utilisées telles quelles ou elles peuvent subir un traitement de surface. Ledit traitement de surface a typiquement pour objectif d’améliorer la dispersibilité de la charge dans la composition organopolysiloxanique et/ou d’améliorer la stabilité thermique de la composition. De plus, le traitement thermique peut permettre d’améliorer la stabilité physique de la composition, en évitant les phénomènes de décantation ou d’exsudation, ou encore d’augmentation de la viscosité. The thermally conductive filler(s) may be used as such or may be surface treated. Said surface treatment typically aims to improve the dispersibility of the filler in the organopolysiloxane composition and/or to improve the thermal stability of the composition. In addition, the heat treatment may improve the physical stability of the composition, by avoiding settling or exudation phenomena, or even an increase in viscosity.
Ledit traitement de surface peut être un traitement thermique, un traitement chimique, un traitement physique, ou leurs combinaisons, notamment la combinaison d’un traitement thermique et d’un traitement chimique. Said surface treatment may be a heat treatment, a chemical treatment, a physical treatment, or their combinations, in particular the combination of a heat treatment and a chemical treatment.
Selon de mode de réalisation préféré, la charge thermoconductrice peut être traitée par des composés organosiliciques habituellement utilisés pour cet usage. La composition silicone réticulable par réaction de poly addition selon l’invention peut donc comprendre un agent de traitement de la charge thermoconductrice. Parmi ces agents figurent : According to the preferred embodiment, the thermally conductive filler can be treated with organosilicon compounds usually used for this purpose. The silicone composition crosslinkable by polyaddition reaction according to the invention can therefore comprise an agent for treating the thermally conductive filler. These agents include:
- les organosiloxanes, notamment les méthylpoly siloxanes tels que l’hexaméthyldisiloxane et- organosiloxanes, in particular methylpolysiloxanes such as hexamethyldisiloxane and
1 ’ octaméthylcyclotétrasiloxane, 1’ octamethylcyclotetrasiloxane,
- les organosilazanes, notamment les méthylpolysilazanes tels que l’hexaméthyldisilazane, le divinyltétraméthyldisilazane et l’hexaméthylcyclotrisilazane, - organosilazanes, in particular methylpolysilazanes such as hexamethyldisilazane, divinyltetramethyldisilazane and hexamethylcyclotrisilazane,
- les chlorosilanes tels que le diméthyldichlorosilane, le triméthylchlorosilane, le méthylvinyldichlorosilane et le diméthylvinylchlorosilane, - chlorosilanes such as dimethyldichlorosilane, trimethylchlorosilane, methylvinyldichlorosilane and dimethylvinylchlorosilane,
- les alcoxysilanes tels que le méthyltriméthoxy silane, le méthyltriéthoxysilane, le phényltriméthoxysilane, l’éthyltriméthoxy silane, le n-propyltriméthoxysilane, un (alkyl en CÔ- Cisjtriméthoxy silane tel que l’octyltriméthoxysilane, le vinyltriméthoxysilane, le diméthylvinyléthoxysilane, le vinyltri(2-méthoxyéthoxy)silane, le vinyltriacétoxy silane, - alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, a (C6-C8)alkyltrimethoxysilane such as octyltrimethoxysilane, vinyltrimethoxysilane, dimethylvinylethoxysilane, vinyltri(2-methoxyethoxy)silane, vinyltriacetoxysilane,
1’ ally Itriméthoxy silane, le butènyltriméthoxysilane, l’hexènyltriméthoxysilane, le gamma- méthacryloxyproyltriméthoxysilane, le diméthyldiméthoxy silane, le diméthyldiéthoxy silane, le diphényldiméthoxy silane, le triméthylméthoxysilane, et le triméthyléthoxy silane. 1' ally Itrimethoxy silane, butenyltrimethoxysilane, hexenyltrimethoxysilane, gamma- methacryloxyproyltrimethoxysilane, dimethyldimethoxy silane, dimethyldiethoxy silane, diphenyldimethoxy silane, trimethylmethoxysilane, and trimethylethoxy silane.
De façon plus préférée, la charge thermoconductrice peut être traitée par un alcoxysilane, notamment un (alkyl en Cô-Cisjtriméthoxy silane, ou par un organosilazane, notamment l’hexaméthyldisilazane (HMDZ) et le divinyltétraméthyldisilazane, ou un mélange de ceux-ci, notamment un mélange d’HMDZ et de divinyltétraméthyldisilazane. Lorsque la charge thermoconductrice est traitée par un agent chimique, notamment par un organosilazane, de l’eau peut être typiquement ajoutée. More preferably, the thermally conductive filler may be treated with an alkoxysilane, especially a (C6-C8)alkyltrimethoxysilane, or with an organosilazane, especially hexamethyldisilazane (HMDZ) and divinyltetramethyldisilazane, or a mixture thereof, especially a mixture of HMDZ and divinyltetramethyldisilazane. When the thermally conductive filler is treated with a chemical agent, especially with an organosilazane, water may typically be added.
La composition silicone réticulable par réaction de polyaddition selon l’invention comprend de préférence de 0,05% à 5% d’un agent de traitement de la charge thermoconductrice, et plus préférentiellement de 0,1% à 3% en poids, par rapport au poids total de la composition silicone réticulable par réaction de polyaddition selon l’invention. The silicone composition crosslinkable by polyaddition reaction according to the invention preferably comprises from 0.05% to 5% of a heat-conducting filler treatment agent, and more preferably from 0.1% to 3% by weight, relative to the total weight of the silicone composition crosslinkable by polyaddition reaction according to the invention.
Un traitement thermique de la charge thermoconductrice peut consister à soumettre ladite charge à une température comprise entre 70°C et 200°C pendant une durée comprise entre 1 heure et 4 heures.A heat treatment of the thermally conductive charge may consist of subjecting said charge to a temperature between 70°C and 200°C for a period between 1 hour and 4 hours.
Selon un mode de réalisation, le traitement de surface peut être réalisé avant l’incorporation de la charge thermoconductrice dans la composition silicone. Selon un mode de réalisation alternatif, le traitement de la charge thermoconductrice peut être réalisé in situ, lors de la préparation de la composition silicone. According to one embodiment, the surface treatment can be carried out before the incorporation of the thermally conductive filler into the silicone composition. According to an alternative embodiment, the treatment of the thermally conductive filler can be carried out in situ, during the preparation of the silicone composition.
La composition silicone réticulable par réaction de polyaddition selon l’invention peut en outre comprendre d’autres composés, en particulier : The silicone composition crosslinkable by polyaddition reaction according to the invention may also comprise other compounds, in particular:
- au moins une charge minérale, notamment de la silice, du quartz, ou un mélange de ceux-ci ; - at least one mineral filler, in particular silica, quartz, or a mixture of these;
- un inhibiteur de réticulation ; - a crosslinking inhibitor;
- un organopolysiloxane non-réactif liquide à température ambiante ; - a non-reactive organopolysiloxane liquid at room temperature;
- une base colorante ; - a coloring base;
- optionnellement d’autres charges. - optionally other charges.
Selon un mode de réalisation préféré, la composition silicone comprend une charge minérale E, qui est de préférence une silice de combustion ou une silice de précipitation. Les charges minérales de type silice ont préférentiellement une surface spécifique, mesurée selon les méthodes BET, d’au moins 10 m2/g, notamment comprise entre 10 m2/g et 400 m2/g, une dimension moyenne des particules primaires inférieure à 0,1 pm (micromètre) et une densité apparente inférieure à 200 g/litre. Très préférentiellement, la charge minérale E est une silice de combustion dont la surface spécifique est comprise entre 10 m2/g et 300 m2/g. According to a preferred embodiment, the silicone composition comprises a mineral filler E, which is preferably a combustion silica or a precipitation silica. The silica-type mineral fillers preferably have a specific surface area, measured according to BET methods, of at least 10 m 2 /g, in particular between 10 m 2 /g and 400 m 2 /g, an average primary particle size of less than 0.1 pm (micrometer) and an apparent density of less than 200 g/liter. Very preferably, the mineral filler E is a combustion silica whose specific surface area is between 10 m 2 /g and 300 m 2 /g.
Les charges minérales de type silice, de préférence hydrophiles, peuvent être incorporées telles quelles dans la composition silicone ou être éventuellement traitées par un agent de compatibilisation. Selon une variante, ces silices peuvent éventuellement être traitées par un ou des composés organosiliciques, par exemple organosilane ou organosilazane, habituellement utilisés pour cet usage. Parmi ces composés, figurent les méthylpolysiloxanes tels que l’hexaméthyldisiloxane, l’octaméthylcyclo- tétrasiloxane, les méthylpolysilazanes tels que l’hexaméthyldisilazane, l’hexaméthylcyclotrisilazane, le tétraméthyldivinyldisilazane, les chlorosilanes tels que le diméthyldichlorosilane, le triméthylchlorosilane, le méthylvinyldichlorosilane, le diméthylvinylchlorosilane, les alcoxysilanes tels que le diméthyldiméthoxysilane, le diméthylvinyléthoxy silane, le triméthylméthoxysilane. Ces composés peuvent être utilisés seuls ou en mélange (voir brevets français FR 1 126 884, FR 1 136 885, FR 1 236 505 et brevet anglais GB 1 024 234). The silica-type mineral fillers, preferably hydrophilic, may be incorporated as such into the silicone composition or may optionally be treated with a compatibilizing agent. According to a variant, these silicas may optionally be treated with one or more organosilicon compounds, for example organosilane or organosilazane, usually used for this purpose. Among these compounds, include methylpolysiloxanes such as hexamethyldisiloxane, octamethylcyclo-tetrasiloxane, methylpolysilazanes such as hexamethyldisilazane, hexamethylcyclotrisilazane, tetramethyldivinyldisilazane, chlorosilanes such as dimethyldichlorosilane, trimethylchlorosilane, methylvinyldichlorosilane, dimethylvinylchlorosilane, alkoxysilanes such as dimethyldimethoxysilane, dimethylvinylethoxy silane, trimethylmethoxysilane. These compounds can be used alone or in mixtures (see French patents FR 1 126 884, FR 1 136 885, FR 1 236 505 and English patent GB 1 024 234).
La silice peut éventuellement être prédispersée dans une huile silicone, de façon à obtenir une suspension. On préfère notamment utiliser une suspension de silice de combustion traitée, notamment par de l’hexaméthyldisilazane, dans une huile polyorganosiloxane, notamment vinylée. The silica may optionally be pre-dispersed in a silicone oil, so as to obtain a suspension. It is particularly preferred to use a suspension of treated combustion silica, in particular with hexamethyldisilazane, in a polyorganosiloxane oil, in particular vinylated.
Alternativement ou en complément, la composition silicone selon invention peut également contenir au moins une autre charge minérale qui est un quartz. Il est utilisé de préférence un quartz naturel broyé avec une granulométrie moyenne inférieure à 10 microns. Le quartz peut éventuellement être traité pour améliorer sa compatibilité avec les organopoly siloxanes. Alternatively or in addition, the silicone composition according to the invention may also contain at least one other mineral filler which is quartz. Preferably, a ground natural quartz with an average particle size of less than 10 microns is used. The quartz may optionally be treated to improve its compatibility with organopolysiloxanes.
D’autres charges minérales peuvent être envisagées, notamment des charges de bourrage, telles que par exemple les terres de diatomées, le carbonate de calcium et/ou le kaolin. Other mineral fillers may be considered, including bulking fillers, such as diatomaceous earth, calcium carbonate and/or kaolin.
Selon un mode de réalisation, la composition silicone réticulable par réaction de polyaddition selon l’invention peut optionnellement comprendre un inhibiteur de réticulation F. La fonction de l’inhibiteur F est de ralentir la réaction de polyaddition. L’inhibiteur de réticulation F peut être choisi parmi les composés suivants : According to one embodiment, the silicone composition crosslinkable by polyaddition reaction according to the invention may optionally comprise a crosslinking inhibitor F. The function of the inhibitor F is to slow down the polyaddition reaction. The crosslinking inhibitor F may be chosen from the following compounds:
- un organopolysiloxane, avantageusement cyclique, et substitué par au moins un alcényle, le tétraméthyltétravinylcyclotétrasiloxane étant particulièrement préféré, - an organopolysiloxane, advantageously cyclic, and substituted by at least one alkenyl, tetramethyltetravinylcyclotetrasiloxane being particularly preferred,
- la pyridine, - pyridine,
- les phosphines et les phosphites organiques, - organic phosphines and phosphites,
- les amides insaturées, - unsaturated amides,
- les maléates alkylés, et - alkylated maleates, and
- les alcools acétyléniques, de préférence, un alcool acétylénique de formule (R1)(R2)C(OH)-C=CH, dans laquelle : - acetylenic alcohols, preferably an acetylenic alcohol of formula (R 1 )(R 2 )C(OH)-C=CH, in which:
- R1 est un radical alkyle linéaire ou ramifié, ou un radical phényle, - R 1 is a linear or branched alkyl radical, or a phenyl radical,
- R2 est un atome d’hydrogène, un radical alkyle linéaire ou ramifié, ou un radical phényle, - R 2 is a hydrogen atom, a linear or branched alkyl radical, or a phenyl radical,
- les radicaux R1, R2 et l’atome de carbone situé en alpha de la triple liaison pouvant éventuellement former un cycle, et - the radicals R 1 , R 2 and the carbon atom located in alpha of the triple bond which can possibly form a cycle, and
- le nombre total d’atomes de carbone contenus dans R1 et R2 étant d’au moins 5, de préférence de 9 à 20. - the total number of carbon atoms contained in R 1 and R 2 being at least 5, preferably from 9 to 20.
Lesdits alcools acétyléniques sont, de préférence, choisis parmi ceux présentant un point d’ébullition supérieur à 250°C. On peut citer à titre d’exemples, les produits suivants qui sont disponibles commercialement : le 1-éthynyl-l-cyclohexanol, le méthyl-3-dodécyne-l-ol-3, le triméthyl-3,7,11- dodécyne- l-ol-3, le diphényl-l,l-propyne-2-ol-l, l’éthyl-3-éthyl-6-nonyne-l-ol-3 et le méthyl-3- pentadécyne- 1 -ol-3. Said acetylenic alcohols are preferably chosen from those having a boiling point above 250°C. Examples include the following products which are commercially available: 1-ethynyl-1-cyclohexanol, methyl-3-dodecyne-1-ol-3, trimethyl-3,7,11- dodecyne-1-ol-3, diphenyl-1,1-propyne-2-ol-1, ethyl-3-ethyl-6-nonyne-1-ol-3 and methyl-3-pentadecyne-1-ol-3.
De préférence, l’inhibiteur de réticulation F est le 1-éthynyl-l-cyclohexanol ou le tétraméthyltétravinylcyclotétrasiloxane. Preferably, the crosslinking inhibitor F is 1-ethynyl-1-cyclohexanol or tetramethyltetravinylcyclotetrasiloxane.
Selon le procédé mis en œuvre pour produire l’élastomère silicone selon l’invention, la présence de l’inhibiteur peut être nécessaire ou pas. Si besoin, un tel inhibiteur de réticulation peut typiquement être présent à raison de 3000 ppm au maximum, de préférence à raison de 100 ppm à 2000 ppm par rapport au poids total de la composition silicone réticulable par réaction de polyaddition selon l’invention. Depending on the process used to produce the silicone elastomer according to the invention, the presence of the inhibitor may or may not be necessary. If necessary, such a crosslinking inhibitor may typically be present at a maximum of 3000 ppm, preferably at a maximum of 100 ppm to 2000 ppm relative to the total weight of the silicone composition crosslinkable by polyaddition reaction according to the invention.
Selon un mode de réalisation, la composition silicone réticulable par réaction de polyaddition selon l’invention peut optionnellement comprendre un organopolysiloxane non-réactif liquide à température ambiante G. Les organopolysiloxanes non-réactifs liquides à température ambiante ont pour fonction de diminuer la viscosité globale de la composition. Dans ce contexte, le terme “non-réactif’ signifie que cet organopolysiloxane ne participe pas à la réaction de polyaddition conduisant à la réticulation de l’élastomère. De préférence, ledit organopolysiloxane non-réactif liquide à température ambiante G est un diorganopolysiloxane linéaire bloqué à chaque extrémité de sa chaîne par un motif triorganosiloxy, dont les radicaux organiques liés aux atomes de silicium, sont choisis parmi les radicaux alkyles ayant de 1 à 8 atomes de carbone. Il peut typiquement s’agir d’un polydiméthysiloxane à terminaisons triméthylsiloxy. L’ organopolysiloxane non-réactif liquide à température ambiante G a de préférence une viscosité comprise entre 50 mPa et 1,000 mPa.s, de préférence entre 50 mPa.s et 500 mPa.s, plus préférentiellement entre 50 mPa.s et 200 mPa.s. La viscosité dynamique est mesurée à 25 °C de manière connue en soi, avec un viscosimètre Brookfield à un gradient de vitesse de cisaillement suffisamment faible pour que la viscosité mesurée soit indépendante du gradient de vitesse. According to one embodiment, the silicone composition crosslinkable by polyaddition reaction according to the invention may optionally comprise a non-reactive organopolysiloxane which is liquid at room temperature G. The non-reactive organopolysiloxanes which are liquid at room temperature have the function of reducing the overall viscosity of the composition. In this context, the term “non-reactive” means that this organopolysiloxane does not participate in the polyaddition reaction leading to the crosslinking of the elastomer. Preferably, said non-reactive organopolysiloxane liquid at room temperature G is a linear diorganopolysiloxane blocked at each end of its chain by a triorganosiloxy unit, the organic radicals of which linked to the silicon atoms are chosen from alkyl radicals having from 1 to 8 carbon atoms. It may typically be a polydimethylsiloxane with trimethylsiloxy terminations. The non-reactive organopolysiloxane liquid at room temperature G preferably has a viscosity of between 50 mPa and 1,000 mPa.s, preferably between 50 mPa.s and 500 mPa.s, more preferably between 50 mPa.s and 200 mPa.s. The dynamic viscosity is measured at 25 °C in a manner known per se, with a Brookfield viscometer at a shear rate gradient sufficiently low so that the measured viscosity is independent of the rate gradient.
La composition silicone réticulable par réaction de polyaddition selon l’invention comprend (en poids par rapport au poids total de la composition silicone) de 0% à 10%, de préférence de 0,1% à 5%, d’un organopolysiloxane non-réactif liquide à température ambiante G. The silicone composition crosslinkable by polyaddition reaction according to the invention comprises (by weight relative to the total weight of the silicone composition) from 0% to 10%, preferably from 0.1% to 5%, of a non-reactive organopolysiloxane liquid at room temperature G.
Selon un mode de réalisation, la composition silicone réticulable par réaction de polyaddition selon la présente invention peut optionnellement comprendre d’autres additifs traditionnellement utilisés dans ce domaine technique par l’homme du métier, par exemple un promoteur d’adhérence, un colorant, un retardateur de feu, un agent rhéologique tel qu’un agent thixotrope, etc.. According to one embodiment, the silicone composition crosslinkable by polyaddition reaction according to the present invention may optionally comprise other additives traditionally used in this technical field by those skilled in the art, for example an adhesion promoter, a colorant, a fire retardant, a rheological agent such as a thixotropic agent, etc.
Selon un mode de réalisation, la composition silicone réticulable par réaction de polyaddition selon la présente invention peut contenir un faible taux de composés organiques volatils, typiquement moins de 100 pgC/g, de préférence moins de 70 pgC/g, ou encore moins de 50 pgC/g. Pour cela, les composés organopolysiloxanes utilisés dans le composition selon la présente invention peuvent être de préférence choisis parmi les composés contenant eux-mêmes un faible taux de composés organiques volatils. According to one embodiment, the silicone composition crosslinkable by polyaddition reaction according to the present invention may contain a low level of volatile organic compounds, typically less than 100 pgC/g, preferably less than 70 pgC/g, or even less than 50 pgC/g. For this, the organopolysiloxane compounds used in the composition according to the present invention may be preferably chosen from compounds themselves containing a low level of volatile organic compounds.
Selon un mode de réalisation, la composition silicone réticulable par réaction de polyaddition selon l’invention comprend (en poids par rapport au poids total de la composition silicone) : According to one embodiment, the silicone composition crosslinkable by polyaddition reaction according to the invention comprises (by weight relative to the total weight of the silicone composition):
- de 5% à 50% d’au moins un organopolysiloxane A présentant, par molécule, au moins un groupe alcényle en C2-C12 lié au silicium, - from 5% to 50% of at least one organopolysiloxane A having, per molecule, at least one C2-C12 alkenyl group linked to silicon,
- de 0,1% à 15% d’au moins un organopolysiloxane B présentant, par molécule, au moins deux motifs SiH, - from 0.1% to 15% of at least one organopolysiloxane B having, per molecule, at least two SiH units,
- de 2 ppm à 400 ppm d’au moins un catalyseur de polyaddition C dérivé du platine (en poids de platine-métal), et - from 2 ppm to 400 ppm of at least one polyaddition catalyst C derived from platinum (by weight of platinum-metal), and
- de 50% à 95% d’une charge thermoconductrice D. - from 50% to 95% of a thermally conductive charge D.
Selon un autre mode de réalisation, la composition silicone réticulable par réaction de polyaddition selon l’invention comprend (en poids par rapport au poids total de la composition silicone) : According to another embodiment, the silicone composition crosslinkable by polyaddition reaction according to the invention comprises (by weight relative to the total weight of the silicone composition):
- de 10% à 40% d’au moins un organopolysiloxane A présentant, par molécule, au moins un groupe alcényle en C2-C12 lié au silicium, - from 10% to 40% of at least one organopolysiloxane A having, per molecule, at least one C2-C12 alkenyl group linked to silicon,
- de 0,5% à 10% d’au moins un organopolysiloxane B présentant, par molécule, au moins deux motifs SiH, - from 0.5% to 10% of at least one organopolysiloxane B having, per molecule, at least two SiH units,
- de 5 ppm à 200 ppm d’au moins un catalyseur de polyaddition C dérivé du platine (en poids de platine-métal), - from 5 ppm to 200 ppm of at least one polyaddition catalyst C derived from platinum (by weight of platinum-metal),
- de 60% à 95% d’une charge thermoconductrice D, - from 60% to 95% of a thermally conductive charge D,
- de 0% à 5% d’une charge minérale E, - from 0% to 5% of a mineral charge E,
- de 0 ppm à 3000 ppm d’un inhibiteur de réticulation F, et - from 0 ppm to 3000 ppm of a crosslinking inhibitor F, and
- de 0% à 10% d’un organopolysiloxane non-réactif liquide à température ambiante G. - from 0% to 10% of a non-reactive organopolysiloxane liquid at room temperature G.
Selon encore un autre mode de réalisation, la composition silicone réticulable par réaction de polyaddition selon l’invention comprend (en poids par rapport au poids total de la composition silicone) : According to yet another embodiment, the silicone composition crosslinkable by polyaddition reaction according to the invention comprises (by weight relative to the total weight of the silicone composition):
- de 10% à 40% d’au moins un organopolysiloxane A présentant, par molécule, au moins un groupe alcényle en C2-C12 lié au silicium, - from 10% to 40% of at least one organopolysiloxane A having, per molecule, at least one C2-C12 alkenyl group linked to silicon,
- de 0,5% à 10% d’au moins un organopolysiloxane B présentant, par molécule, au moins deux motifs SiH, - from 0.5% to 10% of at least one organopolysiloxane B having, per molecule, at least two SiH units,
- de 5 ppm à 200 ppm d’au moins un catalyseur de polyaddition C dérivé du platine (en poids de platine-métal),, - from 5 ppm to 200 ppm of at least one polyaddition catalyst C derived from platinum (by weight of platinum-metal),,
- de 70% à 95% d’une charge thermoconductrice D, - from 70% to 95% of a thermally conductive charge D,
- de 0,01% à 1% d’une charge minérale E, - from 0.01% to 1% of a mineral charge E,
- de 100 ppm à 2000 ppm d’un inhibiteur de réticulation F, et - de 0% à 10%, de préférence de 0,1% à 5%, d’un organopolysiloxane non-réactif liquide à température ambiante G. - from 100 ppm to 2000 ppm of a crosslinking inhibitor F, and - from 0% to 10%, preferably from 0.1% to 5%, of a non-reactive organopolysiloxane liquid at room temperature G.
Selon un mode de réalisation, la composition silicone selon l’invention peut être préparée à partir d’un système bi-composant (ou multi-composant) caractérisé en ce qu’il se présente en deux (ou plus) parties distinctes destinées à être mélangées pour former ladite composition silicone. En particulier, dans le cas des compositions silicones préférées telles que décrites ci-dessus, la composition silicone peut être préparée à partir d’un système bi-composant caractérisé en ce que l’une des parties comprend le catalyseur C et ne comprend pas l’ organopolysiloxane B, tandis que l’autre partie comprend l’ organopolysiloxane B et ne comprend pas le catalyseur C. D’autres systèmes multi-composants peuvent être prévus pour améliorer la durée de stockage et/ou optimiser la viscosité de chacun des composants. Par exemple, la composition silicone selon l’invention peut être préparée à partir d’un système tri-composant caractérisé en ce qu’il se présente en trois parties distinctes destinées à être mélangées pour former ladite composition silicone. According to one embodiment, the silicone composition according to the invention can be prepared from a two-component (or multi-component) system characterized in that it is present in two (or more) distinct parts intended to be mixed to form said silicone composition. In particular, in the case of the preferred silicone compositions as described above, the silicone composition can be prepared from a two-component system characterized in that one of the parts comprises catalyst C and does not comprise organopolysiloxane B, while the other part comprises organopolysiloxane B and does not comprise catalyst C. Other multi-component systems can be provided to improve the storage life and/or optimize the viscosity of each of the components. For example, the silicone composition according to the invention can be prepared from a three-component system characterized in that it is present in three distinct parts intended to be mixed to form said silicone composition.
Selon un mode de réalisation préféré, la composition silicone selon l’invention se présente en deux parties distinctes PI et P2 destinées à être mélangées pour former ladite composition silicone, la partie PI comprenant : According to a preferred embodiment, the silicone composition according to the invention is presented in two distinct parts PI and P2 intended to be mixed to form said silicone composition, the part PI comprising:
- tout ou partie de l’ organopolysiloxane A présentant, par molécule, au moins un groupe alcényle en C2-C12 lié au silicium, - all or part of the organopolysiloxane A having, per molecule, at least one C2-C12 alkenyl group linked to silicon,
- le catalyseur de poly addition C, - the poly addition catalyst C,
- tout ou partie de la charge thermoconductrice D, optionnellement avec l’agent de traitement de la charge thermoconductrice, et la partie P2 comprenant : - all or part of the thermally conductive filler D, optionally with the thermally conductive filler treatment agent, and part P2 comprising:
- optionnellement une partie de l’ organopolysiloxane A présentant, par molécule, au moins un groupe alcényle en C2-C12 lié au silicium, - optionally a part of the organopolysiloxane A having, per molecule, at least one C2-C12 alkenyl group linked to silicon,
- 1’ organopolysiloxane B présentant, par molécule, au moins deux motifs SiH, - organopolysiloxane B having, per molecule, at least two SiH units,
- tout ou partie de la charge thermoconductrice D, optionnellement avec l’agent de traitement de la charge thermoconductrice, - all or part of the thermally conductive filler D, optionally with the thermally conductive filler treatment agent,
- optionnellement l’inhibiteur de réticulation F. - optionally the crosslinking inhibitor F.
La charge thermoconductrice D peut être présente dans la partie PI, dans la partie P2 ou dans les deux parties PI et P2, avec des teneurs identiques ou différentes entre les parties PI et P2. The thermally conductive filler D can be present in part PI, in part P2 or in both parts PI and P2, with identical or different contents between parts PI and P2.
Avantageusement, la charge thermoconductrice D peut être présente dans la partie PI et dans la partie P2 selon une teneur identique. Ainsi, la teneur totale en charge thermoconductrice D reste invariable dans la composition silicone réticulable par réaction de polyaddition quel que soit le taux de mélange des parties PI et P2. Chacune des parties PI et P2 selon la présente invention peut être obtenue en mélangeant les différents composants dans un dispositif approprié connu de l’homme du métier. Selon un mode de réalisation particulièrement avantageux de la présente invention, la partie PI, la partie P2 ou les deux parties PI et P2 peuvent être obtenues à partir d’une composition intermédiaire comprenant tout ou partie de l’organopoly siloxane A et tout ou partie de la charge thermoconductrice D, ainsi qu’optionnellement l’agent de traitement de la charge thermoconductrice. Advantageously, the thermally conductive filler D may be present in the PI part and in the P2 part in an identical content. Thus, the total content of thermally conductive filler D remains invariable in the silicone composition crosslinkable by polyaddition reaction regardless of the mixing rate of the PI and P2 parts. Each of the PI and P2 parts according to the present invention may be obtained by mixing the different components in a suitable device known to those skilled in the art. According to a particularly advantageous embodiment of the present invention, the part PI, the part P2 or both parts PI and P2 can be obtained from an intermediate composition comprising all or part of the organopoly siloxane A and all or part of the thermally conductive filler D, as well as optionally the agent for treating the thermally conductive filler.
La présente invention a également pour objet l’élastomère silicone obtenu ou susceptible d’être obtenu par réticulation de la composition silicone réticulable par réaction de polyaddition telle que définie ci- dessus, le procédé d’obtention dudit élastomère, ainsi que l’utilisation dudit élastomère. The present invention also relates to the silicone elastomer obtained or capable of being obtained by crosslinking the crosslinkable silicone composition by polyaddition reaction as defined above, the process for obtaining said elastomer, as well as the use of said elastomer.
La composition silicone réticulable par réaction de polyaddition telle que définie ci-dessus est particulièrement adaptée à la préparation d’un élastomère silicone ayant des propriétés de thermoconduction. The silicone composition crosslinkable by polyaddition reaction as defined above is particularly suitable for the preparation of a silicone elastomer having thermoconductive properties.
Un objet de la présente invention consiste en un procédé de préparation d’un élastomère silicone thermoconducteur comprenant l’étape consistant à laisser réticuler ladite composition silicone réticulable par réaction de polyaddition pour obtenir ledit élastomère silicone thermoconducteur.An object of the present invention consists of a process for preparing a thermally conductive silicone elastomer comprising the step of allowing said crosslinkable silicone composition to crosslink by polyaddition reaction to obtain said thermally conductive silicone elastomer.
Un autre objet de la présente invention consiste en un procédé de préparation d’un élastomère silicone comprenant les étapes suivantes : a) fournir un système bi-composant comprenant l’ensemble des composants de la composition silicone réticulable par réaction de polyaddition telle que définie ci-dessus ; b) mélanger les deux parties dudit système bi-composant pour obtenir la composition silicone réticulable par réaction de polyaddition ; et c) laisser réticuler ladite composition silicone réticulable par réaction de polyaddition pour obtenir ledit élastomère silicone thermoconducteur. Another object of the present invention consists of a process for preparing a silicone elastomer comprising the following steps: a) providing a two-component system comprising all the components of the silicone composition crosslinkable by polyaddition reaction as defined above; b) mixing the two parts of said two-component system to obtain the silicone composition crosslinkable by polyaddition reaction; and c) allowing said silicone composition crosslinkable by polyaddition reaction to crosslink to obtain said thermally conductive silicone elastomer.
L’étape de réticulation peut avoir une durée variable en fonction de la composition silicone et de la température. Généralement, un élastomère silicone avec de bonnes propriétés est obtenu après quelques minutes ou quelques heures en fonction de la température et de la concentration en catalyseur et en inhibiteur dans la composition silicone. Le mélange des parties du système bi-composant (ou multi-composant) peut avoir lieu typiquement dans un mélangeur (agitateur mécanique à pâles inclinées, mélangeur dynamique basse pression, ou tout autre système classique d’agitation) à température proche de la température ambiante, c’est-à-dire entre 10°C et 40°C. Une augmentation de la température de la composition silicone est parfois observée lors de ce mélange selon le type de mélangeur et le cisaillement appliqué. Si l’on souhaite accélérer la réticulation de la composition silicone, on peut réaliser le mélange à une température plus élevée, avantageusement entre 40°C et 70°C. The crosslinking step can have a variable duration depending on the silicone composition and the temperature. Generally, a silicone elastomer with good properties is obtained after a few minutes or a few hours depending on the temperature and the concentration of catalyst and inhibitor in the silicone composition. The mixing of the parts of the two-component (or multi-component) system can typically take place in a mixer (mechanical stirrer with inclined blades, low-pressure dynamic mixer, or any other conventional stirring system) at a temperature close to room temperature, i.e. between 10°C and 40°C. An increase in the temperature of the silicone composition is sometimes observed during this mixing depending on the type of mixer and the shear applied. If it is desired to accelerate the crosslinking of the silicone composition, the mixing can be carried out at a higher temperature, advantageously between 40°C and 70°C.
Ledit élastomère silicone peut avantageusement être utilisé comme matériau thermoconducteur dans différents domaines techniques, notamment dans le domaine de l’électronique, dans des applications électriques, et dans le domaine de l’automobile. Ledit élastomère silicone peut avantageusement être utilisé comme matériau thermoconducteur d’enrobage (i.e. « potting » selon la terminologie anglo- saxonne), de remplissage (i.e. « gap-filler » selon la terminologie anglo-saxonne) ou matériau thermoconducteur adhésif, notamment pour les batteries, par exemple les batteries des véhicules électriques et des véhicules hybrides, mais aussi les batteries stationnaires. La présente invention a également pour objet une batterie, de préférence un batterie de véhicule électrique ou de véhicule hybride, comprenant l’élastomère silicone thermoconducteur objet de la présente invention comme matériau thermoconducteur d’enrobage, de remplissage ou matériau thermoconducteur adhésif. Dans le domaine de l’électronique, l’élastomère silicone selon l’invention peut avantageusement être utilisé comme matériau thermoconducteur dans les dispositifs 5G. Said silicone elastomer can advantageously be used as a thermally conductive material in various technical fields, in particular in the field of electronics, in electrical applications, and in the automotive field. Said silicone elastomer can advantageously be used as a thermally conductive potting material (i.e. "potting" according to English terminology), filling material (i.e. "gap-filler" according to English terminology) or adhesive thermally conductive material, in particular for batteries, for example batteries of electric vehicles and hybrid vehicles, but also stationary batteries. The present invention also relates to a battery, preferably an electric vehicle or hybrid vehicle battery, comprising the thermally conductive silicone elastomer which is the subject of the present invention as a thermally conductive potting material, filling material or adhesive thermally conductive material. In the field of electronics, the silicone elastomer according to the invention can advantageously be used as a thermally conductive material in 5G devices.
Avantageusement, la composition silicone réticulable par réaction de polyaddition selon la présente invention, ainsi que les partie PI et P2 du système bi-composant P précurseur de la composition silicone réticulable par réaction de polyaddition, possèdent une bonne processabilité. En effet, malgré la présence d’une teneur en charge thermoconductrice élevée, lesdites compositions restent avantageusement suffisamment fluides pour être facilement manipulables, en particulier extrudables.Advantageously, the silicone composition crosslinkable by polyaddition reaction according to the present invention, as well as the parts PI and P2 of the two-component system P precursor of the silicone composition crosslinkable by polyaddition reaction, have good processability. Indeed, despite the presence of a high content of thermally conductive filler, said compositions advantageously remain sufficiently fluid to be easily handled, in particular extrudable.
Il est du mérite des inventeurs d’avoir réussi à déterminer les bonnes caractéristiques de l’organopolysiloxane A permettant d’abaisser la viscosité à 25°C à une à une vitesse de cisaillement de 10 s 1 (qui peut être qualifié de fort cisaillement) ou de 1 s 1 (qui peut être qualifié de faible cisaillement), ainsi que d’abaisser l’indice de thixotropic. It is to the credit of the inventors that they have succeeded in determining the good characteristics of organopolysiloxane A allowing to lower the viscosity at 25°C to one at a shear rate of 10 s 1 (which can be described as high shear) or 1 s 1 (which can be described as low shear), as well as to lower the thixotropic index.
L’élastomère silicone objet de la présente invention, obtenu ou susceptible d’être obtenu par réticulation de la composition silicone réticulable par réaction de polyaddition, présente avantageusement une conduction thermique comprise entre 0,5 W/m.K et 7 W/m.K, de façon préférée comprise entre 0,9 W/m.K et 5 W/m.K, de façon plus préférée comprise entre 1 W/m.K et 3 W/m.K. The silicone elastomer which is the subject of the present invention, obtained or capable of being obtained by crosslinking the crosslinkable silicone composition by polyaddition reaction, advantageously has a thermal conductivity of between 0.5 W/m.K and 7 W/m.K, preferably of between 0.9 W/m.K and 5 W/m.K, more preferably of between 1 W/m.K and 3 W/m.K.
D’autres détails ou avantages de l’invention apparaîtront plus clairement au vu des exemples donnés ci-dessous uniquement à titre indicatif. Other details or advantages of the invention will appear more clearly from the examples given below for information purposes only.
Exemples Examples
Les compositions silicones décrites en exemple ci-dessous ont été obtenues à partir des matières premières suivantes : The silicone compositions described as examples below were obtained from the following raw materials:
Al à A8 : Huiles polydiméthylsiloxanes vinylées bout de chaine dont les spécifications sont données dans les tableaux 2 à 5. Les motifs T ont été ajoutés dans les huiles A3 à A6 par ajout contrôlé d’une résine silicone contenant des motifs siloxyles de type T. Les motifs T ont été ajoutés dans les huiles A7 et A8 par ajout contrôlé d’hexadécyltriméthoxysilane. A1 to A8: End-vinyl polydimethylsiloxane oils whose specifications are given in tables 2 to 5. The T units were added to oils A3 to A6 by controlled addition of a silicone resin containing T-type siloxyl units. The T units were added to oils A7 and A8 by controlled addition of hexadecyltrimethoxysilane.
B1 : Huile hydrogénodiméthylpolysiloxane avec des groupes SiH bout de chaine (a/co), ayant une teneur en groupes vinyles de SiH de 5,7% en poids, viscosité = 8,5 mPa.s B1: Hydrogendimethylpolysiloxane oil with SiH groups at the end of the chain (a/co), having a SiH vinyl group content of 5.7% by weight, viscosity = 8.5 mPa.s
B2 : Huile poly(méthylhydrogéno)(diméthyl)siloxane avec des groupes SiH en milieu et bout de chaine (a/co), ayant une teneur en groupes vinyles de SiH de 7,3% en poids, viscosité = 30 mPa.s C : catalyseur platine de Karstedt, contenant 10% en poids de platine-métal B2: Poly(methylhydrogen)(dimethyl)siloxane oil with SiH groups in the middle and end of the chain (a/co), having a SiH vinyl group content of 7.3% by weight, viscosity = 30 mPa.s C: Karstedt platinum catalyst, containing 10% by weight of platinum metal
D : ATH (trihydrate d’aluminium) en poudre ; D: ATH (aluminum trihydrate) powder;
E : silice de combustion avec traitement hydrophobe dont la surface spécifique est d’environ 15- 45 m2/g ; E: combustion silica with hydrophobic treatment with a specific surface area of approximately 15-45 m2 /g;
F : 2,4,6,8-tétraéthènyl-2,4,6,8-tétraméthylcyclotétrasiloxane. F: 2,4,6,8-tetraethenyl-2,4,6,8-tetramethylcyclotetrasiloxane.
Les analyses ont été effectuées selon les protocoles de mesures décrits ci-après : The analyses were carried out according to the measurement protocols described below:
Viscosité des huiles silicones A : mesurée sur un viscosimètre rotatif Brookfield (aiguille n°l) à une vitesse de 500 tr/min à 25 °C. Viscosity of silicone oils A: measured on a Brookfield rotary viscometer (needle no. 1) at a speed of 500 rpm at 25 °C.
Viscosité des compositions silicones : mesurée sur un rhéomètre Haake à 25 °C, suivant un programme utilisant une rampe de cisaillement montant et descendant, de 0 s 1 à 20 s 1 en 120 s (lere partie) puis de 20 s 1 à 0 s 1 en 120 s (2eme partie). Les valeurs de viscosité relevées sont les valeurs à 10 s 1 et à 1 s 1 obtenues durant la 2eme partie du programme (rampe décroissante). L’installation utilisée est de géométrie plan/plan. Le diamètre du plateau supérieur est de 20 mm. La distance entre les deux plateaux est de 0,500 mm. Viscosity of silicone compositions: measured on a Haake rheometer at 25 °C, following a program using an upward and downward shear ramp, from 0 s 1 to 20 s 1 in 120 s ( 1st part) then from 20 s 1 to 0 s 1 in 120 s ( 2nd part). The viscosity values recorded are the values at 10 s 1 and 1 s 1 obtained during the 2nd part of the program (decreasing ramp). The installation used is of plane/plane geometry. The diameter of the upper plate is 20 mm. The distance between the two plates is 0.500 mm.
Index de thixotropic (TI) : rapport entre la viscosité à 25 °C à une vitesse de cisaillement de 10 s 1 et la viscosité à 25 °C à une vitesse de cisaillement de 1 s'1. Thixotropic index (TI): ratio of viscosity at 25°C at a shear rate of 10 s 1 to viscosity at 25°C at a shear rate of 1 s' 1 .
Teneur en motif siloxyle de type T ([T]) : La teneur en motif siloxyle de type T dans le composé organopolysiloxane A est une teneur en poids de motifs S i O3/2, par rapport au poids total (poids motif T « SiOs/2 » /poids total de l’huile polydiméthylsiloxane A). La valeur indiquée dans les exemples ci- dessous est une valeur théorique calculée à partir des quantités respectives de matières premières mises enjeu lors de la synthèse des huiles polydiméthylsiloxanes Al à A8. T-type siloxyl unit content ([T]): The T-type siloxyl unit content in the organopolysiloxane compound A is a content by weight of SiO3/2 units, relative to the total weight (weight of T-unit “SiOs/2” /total weight of the polydimethylsiloxane oil A). The value indicated in the examples below is a theoretical value calculated from the respective quantities of raw materials used during the synthesis of the polydimethylsiloxane oils A1 to A8.
Mesure de la teneur en groupes OH liés au silicium (1QH1) : La teneur en groupes OH liés au silicium a été mesurée par infrarouge, selon la méthode après deutération décrite dans “Measurement of Trace Silanol in Siloxanes by IR Spectroscopy” par Elmer D. Lipp, Applied Spectroscopy vol. 45, no. 3, 1991, pp. 477-483. En pratique, la courbe de calibration a été construite à partir de solutions standard dont la teneur en groupe OH est connue. La teneur en groupe OH de l’échantillon a été calculée par mesure de la densité optique de la dérivée seconde de la bande des SiOD à 2726 cm'1. Measurement of silicon-bonded OH content (1QH1): The silicon-bonded OH content was measured by infrared, according to the deuterated method described in “Measurement of Trace Silanol in Siloxanes by IR Spectroscopy” by Elmer D. Lipp, Applied Spectroscopy vol. 45, no. 3, 1991, pp. 477-483. In practice, the calibration curve was constructed from standard solutions with known OH content. The OH content of the sample was calculated by measuring the optical density of the second derivative of the SiOD band at 2726 cm' 1 .
Compositions 1 - 13 : Compositions 1 - 13:
Des compositions silicones correspondant aux parties PI et P2 ont été préparées selon le protocole suivant : Pour la partie PI : la charge thermoconductrice D, l’huile silicone A, la charge E, la base colorante et le catalyseur C ont été mélangés selon la concentration indiquée dans le tableau 1 ci- dessous. Pour la partie P2 : la charge thermoconductrice D, l’huile silicone A, des huiles silicones B1 et B2, la charge E et un retardateur F ont été mélangés selon la concentration indiquée dans le tableau 1 ci-dessous. Silicone compositions corresponding to parts PI and P2 were prepared according to the following protocol: For part PI: the thermally conductive filler D, the silicone oil A, the filler E, the coloring base and the catalyst C were mixed according to the concentration indicated in table 1 below. below. For part P2: thermally conductive filler D, silicone oil A, silicone oils B1 and B2, filler E and a retarder F were mixed according to the concentration indicated in Table 1 below.
[Tableau 1] [Table 1]
Des compositions ont ainsi été obtenues avec différentes huiles polydiméthylsiloxanes vinylées bout de chaine Al à A5. Les résultats des analyses sur les parties PI sont donnés dans le tableau 2. Les résultats des analyses pour les parties P2 sont donnés dans le tableau 3. Compositions were thus obtained with different vinylated polydimethylsiloxane oils chain end A1 to A5. The results of the analyses on the PI parts are given in Table 2. The results of the analyses for the P2 parts are given in Table 3.
[Tableau 2] [Table 2]
[Tableau 3] [Table 3]
Par ailleurs, des huiles polydiméthylsiloxanes vinylées bout de chaine A6, A7 et A8 contenant respectivement 642 ppm, 331 ppm et 700 ppm de groupes OH ont été testées. Les résultats des analyses sur les parties PI sont donnés dans le tableau 4. Les résultats des analyses pour les parties P2 sont donnés dans le tableau 5. Furthermore, chain-end vinylated polydimethylsiloxane oils A6, A7 and A8 containing 642 ppm, 331 ppm and 700 ppm of OH groups respectively were tested. The results of the analyses on the PI parts are given in Table 4. The results of the analyses for the P2 parts are given in Table 5.
[Tableau 4] [Table 4]
[Tableau 5] On peut constater que l’utilisation d’une huile A ayant une teneur en motif siloxyle T supérieure à[Table 5] It can be seen that the use of an oil A having a siloxyl unit content T greater than
100 ppm permet avantageusement de diminuer la viscosité des parties PI et P2 de la composition. Cet effet semble renforcé par la présence de groupes OH dans l’huile A. Sur la partie PI, l’utilisation d’une huile A ayant une teneur en motif siloxyle T supérieure à 100 ppm permet également de diminuer son index de thixotropic. 100 ppm advantageously reduces the viscosity of the PI and P2 parts of the composition. This effect seems to be reinforced by the presence of OH groups in oil A. On the PI part, the use of an oil A with a siloxyl unit T content greater than 100 ppm also reduces its thixotropic index.
Claims
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| WO2016071654A1 (en) | 2014-11-07 | 2016-05-12 | Bluestar Silicones France Sas | Novel silicone composition crosslinking catalysts |
| WO2016075414A1 (en) | 2014-11-14 | 2016-05-19 | Bluestar Silicones France Sas | Method of hydrosilylation implementing an organic catalyst derived from germylene |
| WO2018115601A1 (en) | 2016-12-23 | 2018-06-28 | Elkem Silicones France Sas | Cobalt compound useful as catalyst for hydrosilylation, dehydrogenative silylation and crosslinking of silicone compositions |
| WO2019008279A1 (en) | 2017-07-05 | 2019-01-10 | Elkem Silicones France Sas | Iron compound used as a catalyst for hydrosilylation, dehydrogenative silylation and crosslinking of silicone compositions |
| WO2019138194A1 (en) | 2018-01-12 | 2019-07-18 | Elkem Silicones France Sas | Nanoparticles of co complexes of zero-valent metals that can be used as hydrosilylation and dehydrogenative silylation catalysts |
| WO2021260279A1 (en) | 2020-06-25 | 2021-12-30 | Elkem Silicones France Sas | Thermally conductive silicone compositions |
| WO2023283819A1 (en) | 2021-07-14 | 2023-01-19 | Dow Silicones Corporation | Thermal conductive silicone composition |
| WO2023031524A1 (en) | 2021-08-31 | 2023-03-09 | Elkem Silicones France Sas | Hydrosilylation method catalysed by an iron complex |
| WO2023031525A1 (en) | 2021-08-31 | 2023-03-09 | Elkem Silicones France Sas | Hydrosilylation process catalysed by a cobalt complex |
| WO2023139322A1 (en) | 2022-01-18 | 2023-07-27 | Elkem Silicones France Sas | Hydrosilylation process photocatalysed by a manganese complex |
| WO2024146993A1 (en) | 2023-01-06 | 2024-07-11 | Elkem Silicones France Sas | Hydrosilylation process catalysed by a manganese complex |
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2024
- 2024-12-19 WO PCT/FR2024/000121 patent/WO2025133479A1/en active Pending
- 2024-12-19 WO PCT/FR2024/000122 patent/WO2025133480A1/en active Pending
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