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  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
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  • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
  • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
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  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
  • B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • B01J31/121—Metal hydrides
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  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • B01J31/122—Metal aryl or alkyl compounds
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  • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
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  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
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  • C07F7/0803—Compounds with Si-C or Si-Si linkages
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  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0803—Compounds with Si-C or Si-Si linkages
  • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0803—Compounds with Si-C or Si-Si linkages
  • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
  • C07F7/0827—Syntheses with formation of a Si-C bond
  • C07F7/0829—Hydrosilylation reactions
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  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0834—Compounds having one or more O-Si linkage
  • C07F7/0838—Compounds with one or more Si-O-Si sequences
  • C07F7/0872—Preparation and treatment thereof
  • C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
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  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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  • C07F7/1804—Compounds having Si-O-C linkages
  • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
  • C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
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  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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  • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
  • C07F7/1888—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of other Si-linkages, e.g. Si-N
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  • B01J2231/32—Addition reactions to C=C or C-C triple bonds
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  • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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  • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
  • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
  • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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Definitions

• the invention relates to nanoparticles that can be used as catalysts, especially as catalysts for hydrosilylation and dehydrogenating silylation. More specifically, the present invention relates to nanoparticles comprising at least one transition metal at oxidation state 0, selected from the metals of columns 8, 9 and 10 of the periodic table of the elements, and at least one carbonyl ligand.
• Comprising at least one unsaturation reacts with a compound comprising at least one hydrogenosilyl function, i.e., a hydrogen atom bonded to a silicon atom.
• a compound comprising at least one hydrogenosilyl function i.e., a hydrogen atom bonded to a silicon atom.
• the hydrosilylation of unsaturated compounds is carried out by catalysis.
• the catalyst suitable for this reaction is a platinum catalyst.
• the Most of the industrial hydrosilylation reactions are catalyzed by the Karstedt platinum complex, of general formula Pt 2 (divinyltetramethyldisiloxane) 3 (or abbreviated Pt 2 (DVTMS) 3 ):
• this type of catalyst is relatively unstable and evolves during the reaction by forming colloidal species of Pt (0), the size of which is not controlled, which lead to a coloration of the reaction medium and oils obtained from yellow to black.
• One of the objectives of the present invention is therefore to provide a catalyst, particularly suitable for the catalysis of hydrosilylation reactions and dehydrogenating silylation, which is efficient.
• Another object of the invention is to provide a hydrosilylation process using a catalyst that is efficient.
• nanoparticles comprising at least one transition metal at oxidation state 0, chosen from the metals of columns 8, 9 and 10 of the periodic table of the elements, and at least one carbonyl ligand, as a hydrosilylation and / or dehydrogenation silylating catalyst.
• nanoparticles comprising:
• At least one transition metal at the oxidation state selected from the metals of columns 8, 9 and 10 of the periodic table of the elements, and
• the invention also relates to a colloidal suspension comprising nanoparticles.
• the invention also relates to a catalyst comprising nanoparticles or a colloidal suspension comprising nanoparticles.
• the invention also relates to a process for preparing the nanoparticles and / or a colloidal suspension comprising nanoparticles.
• the invention also relates to a hydrosilylation process catalyzed by nanoparticles or a colloidal suspension comprising nanoparticles.
• FIG. 1A represents a photo of STEM HAADF of the colloidal solution comprising iron nanoparticles according to example 1.
• FIG. 1B represents a histogram of the diameter of the iron nanoparticles according to example 1.
• FIG. 2 represents the infrared spectrum of the iron nanoparticles according to example 1 and the iron precursor used.
• FIG. 3 represents the C-NMR spectrum of the iron nanoparticles according to the let example of the iron precursor used.
• FIG. 4 represents the 1H-NMR spectrum of the iron nanoparticles according to Example 1 and n-octylsilane.
• FIG. 5A represents a photo of STEM HAADF of the colloidal solution comprising cobalt nanoparticles according to example 2.
• FIG. 5B represents a histogram of the diameter of the cobalt nanoparticles according to example 2 as a function of their diameter.
• FIG. 6 represents the infrared spectrum of the cobalt nanoparticles according to Example 2 and the cobalt precursor used.
• FIG. 7 represents the C-NMR spectrum of the cobalt nanoparticles according to Example 2 and the cobalt precursor used.
• FIG. 8 represents the 1H-NMR spectrum of the cobalt nanoparticles according to Example 2 and of n-octylsilane.
• FIG. 9 represents the Môssbauer spectrum of the iron nanoparticles according to the example
• silane compound is intended to mean, in the present invention, chemical compounds comprising a silicon atom bonded to four hydrogen atoms or to organic substituents.
• polysilane is meant in the present invention chemical compounds having at least one oSi-Sio pattern.
• hydrosilane compound in the present invention the chemical compounds belonging to the group of silanes, thus comprising at least one silicon atom, and comprising at least one hydrogen atom bonded to the silicon atom.
• organopolysiloxane in the present invention the chemical compounds having at least one oSi-O-Sio unit.
• alkyl is meant a hydrocarbon chain, linear or branched, comprising from 1 to 40 carbon atoms, preferably from 1 to 20 carbon atoms, more preferably from 1 to 10 carbon atoms.
• An alkyl group may be selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, n-butyl, n-pentyl, isoamyl and 1,1-dimethylpropyl.
• cycloalkyl is meant according to the invention a monocyclic or polycyclic saturated hydrocarbon group, preferably monocyclic or bicyclic, containing from 3 to 20 carbon atoms, preferably from 5 to 8 carbon atoms.
• the multiple ring nuclei may be attached to each other by a covalent bond and / or a spiral atom and / or be condensed to each other.
• Cycloalkyl may be selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantane and norborane.
• aryl is meant according to the invention an aromatic hydrocarbon group containing from 5 to 18 carbon atoms, monocyclic or polycyclic.
• An aryl group may be selected from the group consisting of phenyl, naphthyl, anthracenyl and phenanthryl.
• halogen atom is meant according to the invention an atom selected from the group consisting of fluorine, chlorine, bromine and iodine.
• heteroaryl is meant according to the invention an aryl group in which at least one carbon atom has been substituted by a heteroatom selected from O, N, S and P.
• a heteroaryl group may be selected from the group consisting of pyranyl , furanyl, pyridinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, isothiazolyl, isoxazolyl and indolyl.
• heterocycloalkyl is meant according to the invention a cycloalkyl group in which at least one carbon atom has been substituted by a heteroatom selected from O, N, S and P.
• the heterocycloalkyl comprises from 5 to 10 members.
• a heterocycloalkyl group may be the oxiranyl monocyclic group or the epoxycyclohexyl bicyclic group.
• alkoxy is meant according to the invention an alkyl group as defined above bonded to an oxygen atom.
• An alkoxy group may be selected from the group consisting of methoxy, ethoxy, propoxy and butoxy.
• aryloxy is meant according to the invention an aryl group as defined above bonded to an oxygen atom.
• An aryloxy group may be for example the phenoxy group.
• cycloalkoxy is meant according to the invention a cycloalkyl group as defined above bonded to an oxygen atom.
• alkylsilyl is meant according to the invention an alkyl group as defined above bonded to a silicon atom.
• alkoxysilyl is meant according to the invention an alkoxy group as defined above bonded to a silicon atom.
• the present invention relates to nanoparticles comprising:
• At least one transition metal at the oxidation state selected from the metals of columns 8, 9 and 10 of the periodic table of the elements, and
• the metals of columns 8, 9 and 10 of the periodic table of elements are preferably iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium ( Rh), iridium (Ir), nickel (Ni), palladium (Pd) and platinum (Pt).
• the nanoparticles comprise at least one metal chosen from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt, and more preferably in the group consisting of Fe, Co and Ni, or in the group consisting of Fe and Co.
• the nanoparticles may also comprise several metals chosen from the metals of columns 8, 9 and 10 of the periodic table of the elements.
• the nanoparticles may, for example, comprise 2 or 3 metals. It is thus possible to have bimetallic or trimetallic nanoparticles, such as nanoparticles comprising Fe and Co metals, or Fe and Ni metals, or Co and Ni metals, or even nanoparticles comprising Fe, Co and Ni metals.
• the metal or metals contained in the nanoparticles are at oxidation state 0.
• the nanoparticles also include at least one carbonyl (CO) ligand.
• This carbonyl ligand is coordinated to at least one metal atom of columns 8, 9 or 10 of the periodic table.
• This ligand can be coordinated on the surface of the nanoparticles.
• the presence of the carbonyl ligand can be determined by infrared spectroscopy (IR), or by 13 C-NMR.
• the nanoparticles also comprise at least one silicide.
• silicide means chemical compounds comprising a silicon atom bonded to at least one metal atom selected from the metals of columns 8, 9 and 10 of the periodic table of the elements.
• the silicide also comprises at least one Si-C bond.
• the silicide may be chosen from the compounds of formula (I):
• the symbol (s) Y which may be identical or different, represents a metal chosen from the metals of columns 8, 9 and 10 of the periodic table of elements, preferably a metal chosen from Fe, Co and Ni, and even more preferentially Fe and Co;
• the symbol (s) Z 4 which may be identical or different, represent a monovalent hydrocarbon group having from 1 to 18 carbon atoms, optionally substituted by heteroatoms or by radicals comprising heteroatoms, and preferably chosen from the group consisting of by the alkyl groups having 1 to 18 carbon atoms inclusive and aryl groups having 6 to 12 carbon atoms, and even more preferably selected from the group consisting of alkyl groups having 4 to 12 carbon atoms inclusive;
• the symbol (s) Z 4 which may be identical or different, may represent a linear alkyl group having 4 to 12 carbon atoms inclusive.
• the linear alkyl groups having 4 to 12 carbon atoms inclusive there may be mentioned n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n -dodécyle.
• q 1 and the symbol Z 4 represents an n-octyl group.
• the size of the nanoparticles can be variable.
• the nanoparticles have an average diameter less than or equal to 50 nm, or less than or equal to 10 nm. Even more preferably, the nanoparticles have an average diameter less than or equal to 10 nm, or less than or equal to 5 nm, or less than or equal to 3 nm.
• the average diameter may be between 0.5 and 10 nm, or between 0.5 and 5 nm, or between 0.75 and 3 nm.
• the average diameter of the nanoparticles may, for example, be determined by transmission electron microscopy.
• the nanoparticles have an average diameter less than or equal to 10 nm, and comprise:
• At least one metal selected from the metals of columns 8, 9 and 10 of the periodic table of the elements;
• At least one silicide is at least one silicide.
• the nanoparticles have an average diameter less than or equal to 5 nm, and comprise:
• the symbol (s) Y which may be identical or different, represents a metal chosen from the metals of columns 8, 9 and 10 of the periodic table of elements, preferably a metal chosen from Fe, Co and Ni;
• the symbol (s) Z 4 which may be identical or different, represent a monovalent hydrocarbon group having from 1 to 18 carbon atoms, optionally substituted by heteroatoms or by radicals comprising heteroatoms, and preferably chosen from the group consisting of with alkyl groups having 1 to 18 carbon atoms inclusive and aryl groups having 6 to 12 carbon atoms, and even more preferably selected from the group consisting of alkyl groups having 4 to 12 carbon atoms inclusive;
• the nanoparticles are not paramagnetic.
• the nanoparticles have an average diameter less than or equal to 50 nm, and comprise:
• At least one metal selected from the metals of columns 8, 9 and 10 of the periodic table of the elements;
• At least one silicide preferably a silicide selected from the compounds of formula (I):
• the symbol (s) Y which may be identical or different, represents a metal chosen from the metals of columns 8, 9 and 10 of the periodic table of elements, preferably a metal chosen from Fe, Co and Ni;
• the invention also relates to a colloidal suspension comprising nanoparticles as described above.
• the nanoparticles may be suspended in an organic solvent, preferably an aprotic solvent.
• the solvent may be chosen from the group consisting of:
• aromatics preferentially toluene
• alkanes preferentially pentane
• the ethers preferentially THF
• the nanoparticles may also be suspended in a silicone oil, preferably a silicone oil having a dynamic viscosity less than or equal to 100000 mPa.s at 25 ° C.
• the nanoparticles can be suspended in a silicone oil as follows:
• This colloidal suspension may have a starting metal concentration of between 1 and 100 m ⁇ / ml, preferably between 10 and 50 pmol / ml.
• the subject of the invention is also a catalyst comprising transition metal nanoparticles with oxidation state 0 as described above or a suspension colloidal as described above.
• This catalyst may be a hydrosilylation and / or dehydrogenation silylation catalyst.
• This catalyst can also be an isomerization catalyst for alkenes.
• the subject of the invention is also the use of the transition metal nanoparticles at oxidation state 0 as described above or a colloidal suspension as described above as a catalyst, preferably as a hydrosilylation catalyst and / or dehydrogenating silylation and / or isomerization of alkenes.
• the invention also relates to a process for preparing nanoparticles or a colloidal suspension comprising nanoparticles.
• This method comprises a step of mixing at least one metal complex, chosen from transition metal carbonyls of columns 8, 9 and 10 of the periodic table of the elements, with at least one silane in a solvent, under an inert atmosphere and / or under hydrogen.
• the silane will react with the metal complex to form a silicide.
• the metal complex is chosen from the transition metal carbonyls of columns 8, 9 and 10 of the periodic table of the elements, it is therefore a complex of a transition metal chosen from the metals of columns 8, 9 and Of the periodic table of elements comprising at least one carbonyl ligand.
• it is a carbonyl iron, cobalt or nickel, among which may be mentioned: Fe 3 (CO) 2 , Fe 2 (CO) 9, Fe (CO) 5, Co 2 (CO ) 8 , Co 4 (CO) i 2 and Ni (CO) 4 .
• the metal complex is chosen from carbonyl iron or cobalt.
• the silane comprises at least one Si-C bond and at least one Si-H bond. It is preferably a silane of formula (II):
• the amount of silane used in the process is at least 0.01 molar equivalents relative to the metal included in the metal complex used. This amount may be between 0.01 and 5 molar equivalents relative to the metal included in the metal complex used. Preferably, this amount is between 0.01 and 1, and even more preferably between 0.05 and 0.5 molar equivalents relative to the metal included in the metal complex used.
• the amount of silane can influence the size of the nanoparticles.
• the amount of silane is between 0.01 and 1 molar equivalent relative to the metal included in the metal complex, preferably between 0.05 and 0.5 molar equivalents.
• the solvent is an organic solvent, preferably an aprotic solvent.
• the solvent may be chosen from the group consisting of:
• aromatics preferentially toluene
• alkanes preferentially pentane
• the ethers preferentially THF
• the process for preparing the nanoparticles is carried out under an inert atmosphere and / or under hydrogen.
• inert atmosphere is meant a non-reactive gas under the reaction conditions.
• Non-reactive gases include dinitrogen and noble gases (helium, argon, krypton and xenon).
• the process is carried out under nitrogen or under argon.
• the mixing is carried out at a temperature below 140 ° C., preferably between 10 and 135 ° C., between 10 and 120 ° C., or between 10 and 90 ° C.
• the mixture is produced at room temperature.
• the mixture is produced under a hydrogen pressure of between 1 and 10 bar, preferably between 1 and 5 bar.
• the mixing step lasts at least 30 minutes, preferably between 1 and 25 hours.
• the mixing step lasts at least 15 hours, preferably between 15 and 25 hours.
• the invention also relates to nanoparticles and / or a colloidal suspension comprising nanoparticles that can be obtained by the method described above.
• the present invention also relates to a process for preparing hydrosilylation and / or dehydrogenating silylation products by reaction
• said process being characterized by being catalyzed by nanoparticles and / or a colloidal suspension comprising nanoparticles as described above.
• the unsaturated compound A according to the invention is a compound comprising at least one unsaturation which is not part of an aromatic ring.
• Compound A comprises in particular at least one alkene function and / or an alkyne function. Any compound comprising at least one alkene function and / or an alkyne function can be used in the process according to the invention, insofar as it does not contain a reactive chemical function which can hinder or even prevent the hydrosilylation reaction.
• compound A comprises one or more alkene functional groups and from 2 to 40 carbon atoms. It may further comprise 1 to 20 heteroatoms chosen from N, P, O, S, F, Cl, Br and I. When the compound A comprises more than one alkene functional group, these may or may not be conjugated.
• compound A comprises one or more alkyne functions and from 2 to 40 carbon atoms. It may further comprise 1 to 20 heteroatoms chosen from N, P, O, S, F, Cl, Br and I. When the compound A comprises several alkyne functions, these may or may not be conjugated.
• Compound A can be chosen from compounds of formula (III) or (IV):
• R 1 , R 2 , R 3 and R 4 represent, independently of each other
• halogen atom chosen from fluorine, chlorine, bromine and iodine; an alkyl group;
• these groups may themselves be substituted on their (their) part (s) alkyl (s) and / or cycloalkyl (s) and / or aryl (s) by:
• R 1 , R 2 , R 3 and R 4 together with the carbon atoms to which they are bonded form one or more cycloalkyl, heterocycloalkyl, aryl or heteroaryl groups, these groups, cycloalkyl, heterocycloalkyl, aryl and heteroaryl groups; which may be substituted by one or more Cl-alkyl groups C8, optionally halogenated; by one or more C1-C8 alkoxy groups, optionally halogenated; by one or more aryl groups, optionally halogenated; by one or more halogen atoms; by one or more carboxylic acid groups; by one or more ester groups; by one or more ether groups, by one or more urea groups; by one or more amide groups; by one or more sulfonamide groups; by one or more imide groups; by one or more cyano groups; by one or more aldehyde groups; by one or more ketone functions; by one or more alcohol groups
• R 1 , R 2 , R 3 and R 4 being as defined above, and mixtures thereof.
• R 1 , R 2 , R 3 and R 4 represent, independently of one another:
• a C1 to C16 alkyl group optionally substituted by a hydroxyl group or a halogen atom;
• a phenyl optionally substituted with a C1-C4 alkyl group, with a halogen, with a C1-C4 alkyl group itself substituted with one or more halogens, with a C1-C4 alkoxy group or with an amine function; optionally substituted once or twice with a C1 to C4 alkyl group;
• acyloxy group in particular acetyloxy
• a primary amide group in particular not substituted on the nitrogen or substituted once or twice with a C1-C4 alkyl group;
• R 1 may be a hydrogen atom
• R 3 may represent a substituent other than a hydrogen atom
• R 2 and R 4 may furthermore be hydrogen atoms.
• the compound (A) may also be chosen from the group consisting of:
• alkenes preferably octene and more preferably 1-octene
• non-conjugated dienes and preferably hexadiene or octadiene;
• allyl and piperidine ether and preferably sterically hindered allyl and piperidine ether;
• styrene and preferably alpha-methyl styrene
• chlorinated alkenes and preferably allyl chloride
• fluorinated alkenes and preferably 4,4,5,5,6,6,7,7,7-nonafluoro-1-hepttene, and mixtures thereof.
• the compound (A) may also be chosen from compounds comprising a plurality of alkene functional groups, preferably two or three alkene functional groups, and particularly preferably chosen from the following compounds:
• Compound (A) may therefore also comprise chemical functions which will make it possible to modify the compound obtained chemically as a result of the hydrosilylation reaction.
• hydrosilylation of compounds comprising both one or more ethylenic double bonds and one or more acetylenic triple bonds is also contemplated within the scope of the invention.
• the unsaturated compound A is chosen from organopolysiloxane compounds comprising units of formula (V):
• radicals Z which are identical or different, represent a linear or branched alkenyl or alkynyl radical having from 2 to 6 carbon atoms;
• radicals U which are identical or different, represent a hydrocarbon radical having from 1 to 12 carbon atoms
• U may represent a monovalent radical selected from the group consisting of alkyl groups having 1 to 8 carbon atoms. carbon, optionally substituted by at least one halogen atom such as chlorine or fluorine, cycloalkyl groups having 3 to 8 carbon atoms and aryl groups having 6 to 12 carbon atoms.
• U may advantageously be selected from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl.
• Said organopolysiloxancs may be oils with a dynamic viscosity of the order of 10 to 100000 mPa.s at 25 ° C., generally of the order of 10 to 70000 mPa.s at 25 ° C., or viscosity-dynamic gums of 25.degree. order of 1,000,000 mPa.s or more at 25 ° C.
• organopolysiloxanes may have a linear, branched or cyclic structure. Their degree of polymerization is preferably between 2 and 5000.
• linear polymers consist essentially of "D" siloxyl units selected from the group consisting of Z 2 SiO 2/2 , ZUSiO 2/2 and U 2 SiO 2/2 siloxyl units, and siloxyl "M” units selected from the group consisting of siloxyl units ZU 2 SiOi / 2 , Z 2 USiOi / 2 and Z 3 SiOi / 2 .
• Z and U are as described above.
• terminal "M” units mention may be made of trimethylsiloxy, dimethylphenylsiloxy, dimethylvinylsiloxy or dimethylhexenylsiloxy groups.
• D units mention may be made of dimethylsiloxy, methylphenylsiloxy, methylvinylsiloxy, methylbutenylsiloxy, methylhexenylsiloxy, methyldecenylsiloxy or methyldecadienylsiloxy groups.
• linear organopolysiloxanes which may be unsaturated compounds A according to the invention are: a poly (dimethylsiloxane) with dimethylvinylsilyl ends;
• dimethylvinylsilyl-terminated poly dimethylsiloxane-co-methylvinylsiloxane
• the cyclic organopolysiloxanes which can also be unsaturated compounds A according to the invention are, for example, those consisting of "D" siloxyl units of the following formulas: Z 2 SiO 2/2 , U 2 SiO 2/2 or ZUSiO 2/2 , which may be of the dialkylsiloxy, alkylarylsiloxy, alkylvinylsiloxy or alkylsiloxy type.
• the said cyclic organopolysiloxanes have a viscosity of the order of 10 to 5000 mPa.s at 25 ° C.
• a second organopolysiloxane compound comprising, per molecule, at least two C 2 -C 6 alkenyl radicals bonded to silicon atoms, different from the organopolysiloxane compound.
• said second organopolysiloxane compound being preferably divinyltetramethylsiloxane (DVTMS).
• the organopolysiloxane compound A has a mass content of Si-vinyl unit of between 0.001 and 30%, preferably between 0.01 and 10%.
• silicone resins comprising at least one vinyl radical.
• silicone resins may be chosen from the group consisting of the following silicone resins:
• Vl siloxyl unit of formula (R) 2 (vinyl) SiOi / 2
• Vl siloxyl unit of formula (R) (vinyl) Si0 2/2
• the groups R which may be identical or different, are monovalent hydrocarbon-based groups chosen from alkyl groups having from 1 to 8 carbon atoms inclusive, such as methyl, ethyl, propyl and 3,3,3-trifluoropropyl groups, and aryl groups such as as xylyl, tolyl and phenyl.
• the R groups are methyls.
• the process according to the invention also implements a compound B comprising at least one hydrogenosilyl function, that is to say at least one hydrogen atom directly bonded to a silicon atom (ie at least one Si-H group).
• the compound B comprising at least one hydrogenosilyl function is chosen from the group consisting of:
• an organopolysiloxane compound comprising at least one hydrogen atom bonded to a silicon atom, preferably an organopolysiloxane compound comprising, per molecule, at least two hydrogenosilyl functions, and
• the silicon atoms of the compounds (B) are bonded at most to a hydrogen atom.
• the compound (B) can be a hydrogenosilane compound.
• the hydrogenosilane compound according to the invention comprises less than 5 silicon atoms.
• Any hydrogenosilane compound can be used in the process according to the invention, insofar as it does not contain a reactive chemical function which can hinder or even prevent the hydrosilylation reaction.
• the hydrogenosilane compound may be chosen from compounds of formula (VII):
• R represents, independently of each other, a hydrogen atom; a halogen atom, preferably chlorine; an alkyl group optionally substituted with one or more aryl or cycloalkyl groups, with one or more halogen atoms and / or with one or more ketone functions; a cycloalkyl group optionally substituted with one or more alkyl groups and / or one or more halogen atoms; or an aryl group optionally substituted by one or more alkyl groups and / or one or more halogen atoms;
• R - R ' represents, independently of each other, an alkyl group optionally substituted with one or more aryl or cycloalkyl groups, with one or more halogen atoms and / or with a ketone function; a cycloalkyl group optionally substituted with one or more alkyl groups and / or one or more halogen atoms; or an aryl group optionally substituted by one or more alkyl groups and / or one or more halogen atoms;
• R represents, independently of each other, a hydrogen atom; a halogen atom, preferably chlorine; an alkyl group optionally substituted with one or more aryl or cycloalkyl groups and / or with one or more halogen atoms; a cycloalkyl group optionally substituted with one or more alkyl groups and / or one or more halogen atoms; or an aryl group optionally substituted by one or more alkyl groups and / or one or more halogen atoms; and
• Compound B may also be an organopolysiloxane compound comprising at least one hydrogen atom bonded to a silicon atom.
• the organopolysiloxane compound comprises at least two silicon atoms, preferably at least 3 silicon atoms or more.
• Said compound B may advantageously be an organopolysiloxane comprising at least one unit of formula (VIII):
• radicals U which are identical or different, represent a hydrocarbon radical having from 1 to 12 carbon atoms
• U may represent a monovalent radical chosen from the group consisting of an alkyl group having 1 to 8 carbon atoms, optionally substituted with at least one halogen atom such as chlorine or fluorine, alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms and aryl groups having 6 to 12 carbon atoms.
• U may advantageously be selected from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl.
• These organopolysiloxanes may have a linear, branched or cyclic structure.
• the degree of polymerization is preferably greater than or equal to 2. More generally, it is less than 5000.
• siloxyl units "D" chosen from the following units of formula U 2 SiO 2/2 or UHSiO 2/2 , and
• siloxy units "M” chosen from the units of the following formulas SiO 3 U / 2 U 2 or HSiOi / 2.
• linear organopolysiloxanes can be oils of dynamic viscosity of the order of 1 to 100,000 mPa.s at 25 ° C and more generally of the order of 10 to 5000 mPa.s at 25 ° C.
• organopolysiloxanes which may be compounds B according to the invention comprising at least one hydrogen atom bonded to a silicon atom are:
• cyclic organopolysiloxanes consist of "D" siloxyl units of the following formulas U 2 SiO 2/2 and UHSiO 2/2 , which may be of the dialkylsiloxy or alkylarylsiloxy type or of UHSiO 2 units. / 2 only. They then have a viscosity of the order of 1 to 5000 mPa.s.
• compound B is an organopolysiloxane compound comprising, per molecule, at least two and preferably three hydrogenosilyl functions (Si-H).
• organohydrogenpolysiloxane compound B is particularly suitable for the invention as organohydrogenpolysiloxane compound B.
• ⁇ d ⁇ 200 preferably 20 ⁇ d ⁇ 100, and 2 ⁇ e ⁇ 90, preferably 10 ⁇ e ⁇ 70.
• the organohydrogenpolysiloxane compound B has an SiH mass content of between 0.2 and 91%, preferably between 0.2 and 50%.
• compound B can be an organic polymer comprising hydrogenosilyl functions in terminal positions.
• the organic polymer may for example be a polyoxoalkylene, a saturated hydrocarbon polymer or a poly (meth) acrylate.
• Organic polymers comprising reactive functional groups in terminal positions are described in particular in patent applications ETS 2009/0182099 and ETS 2009/0182091.
• the unsaturated compound A and the compound B comprising at least one hydrogenosilyl function to be one and the same compound, comprising on the one hand at least one alkene function and / or one alkyne function, and secondly at least one hydrogen atom bonded to a silicon atom.
• This compound can then be called "bifunctional", and it is likely to react on itself by hydrosilylation reaction.
• the invention can therefore also relate to a process for hydrosilylation of a bifunctional compound with itself, said compound bifunctional comprising on the one hand at least one alkene function and / or an alkyne function, and on the other hand at least one silicon atom and at least one hydrogen atom bonded to the silicon atom, said process being characterized by the fact that it is catalyzed by nanoparticles and / or a colloidal suspension comprising nanoparticles as described above.
• organopolysiloxanes which may be bifunctional compounds are: a dimethylvinylsilyl-terminated poly (dimethylsiloxane-co-hydrogenomethylsiloxane-co-vinylmethylsiloxanes);
• the hydrosilylation process according to the present invention can be carried out at a temperature of between 10 and 150 ° C. According to one embodiment, the hydrosilylation process is carried out at a temperature of between 80 and 140 ° C. According to another embodiment, the hydrosilylation process is carried out at a temperature of between 15 and 60 ° C. According to one embodiment, the hydrosilylation process is carried out at ambient temperature.
• ambient temperature in the present invention a temperature of between 15 and 25 ° C.
• the hydrosilylation process according to the invention can be carried out under an inert atmosphere, for example under nitrogen.
• the hydrosilylation process according to the invention can be carried out under UV radiation.
• the process according to the invention can be carried out in the presence or absence of solvent. According to a preferred embodiment, the process according to the invention is carried out in the absence of a solvent. According to a variant of the invention, one of the reagents, for example the unsaturated compound A, can act as a solvent.
• the relative amount of compound A and compound B can be controlled so as to ensure the reaction rate of unsaturations with desired hydrogenosilyl functions.
• the molar ratio R of the hydrogenosilyl functions of the compounds B to the alkenes and alkynes of the compounds A is between 0.1: 5 and 5: 0.1, preferably between 0.5: 3 and 3: 0.5, and more preferably between 1: 2 and 2: 1.
• the molar ratio R of the hydrogenosilyl functions of the compounds B on the alkenes and alkynes functions of the compounds A is strictly greater than 1.
• the hydrogenosilyl functions are then in excess with respect to the unsaturated functions.
• the hydrosilylation process is then qualified as partial.
• partial functionalization can be used for example to obtain silicone oils with hydrogenosilyl functions and epoxy functions.
• the molar ratio of the hydrogenosilyl functions of the compounds B to the alkenes and alkynes of the compounds A is less than or equal to 1.
• the hydrogenosilyl functions are then in default with respect to the unsaturated functions. This is the case when the unsaturated compound A acts as a solvent.
• the molar concentration of metal originating from the nanoparticles is from 0.001% to 10%, preferably from 0.01% to 5%, and more preferably from 0.05% to 3%. relative to the number of total moles of unsaturations carried by the unsaturated compound A.
• the transition metal nanoparticles with oxidation degree 0 comprise at least one metal chosen from Fe, Co and Ni, and, in the process according to the invention, no compounds based on platinum, palladium, ruthenium or rhodium.
• the compounds A and B used are chosen from organopolysiloxanes as defined above.
• a three-dimensional network is formed, which leads to the hardening of the composition.
• Crosslinking involves a gradual physical change of the medium constituting the composition. Therefore, the process according to the invention can be used to obtain elastomers, gels, foams, etc.
• a cross-linked silicone material Y is obtained.
• Cross-linked silicone material is understood to mean any silicone-based product obtained by crosslinking and / or hardening of compositions comprising organopolysiloxanes having at least two unsaturated bonds and organopolysiloxanes having at least two three hydrogenosilyl units.
• the crosslinked silicone material Y may for example be an elastomer, a gel or a foam.
• additives for heat resistance, resistance to oils or fire resistance for example metal oxides.
• the charges possibly provided are preferably mineral. They can be especially siliceous. As for siliceous materials, they can act as reinforcing or semi-reinforcing filler.
• the reinforcing siliceous fillers are chosen from colloidal silicas, silica powders for combustion and precipitation, or mixtures thereof. These powders have an average particle size generally less than 0.1 ⁇ m (micrometers) and a BET specific surface area greater than 30 m 2 / g, preferably between 30 and 350 m 2 / g.
• Semi-reinforcing siliceous fillers such as diatomaceous earth or ground quartz can also be used.
• non-siliceous mineral materials they can be used as semi-reinforcing mineral filler or stuffing.
• these non-siliceous fillers that can be used alone or as a mixture are carbon black, titanium dioxide, oxide of aluminum, hydrated alumina, expanded vermiculite, unexpanded vermiculite, calcium carbonate optionally surface-treated with fatty acids, zinc oxide, mica, talc, iron oxide, barium sulphate and slaked lime.
• These fillers have a particle size generally of between 0.001 and 300 ⁇ m (micrometers) and a BET surface area of less than 100 m 2 / g.
• the fillers used may be a mixture of quartz and silica. Charges can be processed by any suitable product. In terms of weight, it is preferred to use a quantity of filler of between 1% and 50% by weight, preferably between 1% and 40% by weight relative to all the constituents of the composition.
• adhesion promoters are widely used in silicone compositions.
• one or more adhesion promoters chosen from the group consisting of:
• alkoxylated organosilanes containing, per molecule, at least one C 2 -C 6 alkenyl group selected from the products of the following general formula (Dl):
• R 1 , R 2 and R 3 are hydrogenated or hydrocarbon radicals that are identical to or different from each other and represent a hydrogen atom, a linear or branched C 1 -C 4 alkyl or a phenyl optionally substituted by at least one alkyl group; Ci-C 3 ,
• U is a linear or branched C 1 -C 4 alkylene
• R 4 and R 5 are identical or different radicals and represent a linear or branched C 1 -C 4 alkyl
• organosilicon compounds comprising at least one epoxy radical chosen from:
• R 6 is a linear or branched C 1 -C 4 alkyl radical
• R 7 is a linear or branched C 1 -C 4 alkyl radical
• y 0, 1, 2 or 3
• R 8 , R 9 , R 10 which are identical or different radicals representing a hydrogen atom or a linear or branched C 1 -C 4 alkyl
• R 8 and R 9 or R 10 may alternatively constitute, together with the two epoxy-bearing carbons, an alkyl ring having from 5 to 7 members, or b) the products (D.2b) consisting of epoxyfunctional polydiorganosiloxanes comprising:
• X is the radical as defined above for the formula (D.2 a)
• G is a monovalent hydrocarbon group selected from alkyl groups having from 1 to 8 carbon atoms inclusive, optionally substituted with at least one halogen atom, and as well as from aryl groups containing between 6 and 12 carbon atoms,
• r 0, 1, 2 or 3.
• organosilicon compounds comprising at least one hydrogenosilyl function and at least one epoxy radical and
• metal chelates M and / or metal alkoxides of general formula:
• M is selected from the following list: Ti, Zr, Ge, Li or Mn, and even more preferably the metal M is titanium. It may be associated, for example, an alkoxy radical of butoxy type.
• Silicone resins are well known and commercially available branched organopolysiloxane oligomers or polymers. They have, in their structure, at least two different units chosen from those of formula R 3 SiOy 2 (unit M), R 2 SiO 2/2 (unit D), RSiO 3/2 (unit T) and Si0 4/2 (Q pattern), at least one of these patterns being a T or Q pattern.
• the radicals R are identical or different and are chosen from linear or branched C1-C6 alkyl, hydroxyl, phenyl and 3,3,3-trifluoropropyl radicals.
• alkyl radicals methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals.
• oligomers or branched organopolysiloxane polymers examples include MQ resins, MDQ resins, TD resins and MDT resins, the hydroxyl functions that may be borne by the M, D and / or T units.
• resins which are particularly suitable include hydroxylated MDQ resins having a weight content of hydroxyl group of between 0.2 and 10% by weight.
• composition X comprising:
• At least one compound B comprising at least one hydrogenosilyl function as defined above, and
• nanoparticles or a colloidal suspension comprising nanoparticles as defined above are examples of nanoparticles or a colloidal suspension comprising nanoparticles as defined above.
• composition X is a crosslinkable composition comprising:
• At least one unsaturated compound A comprising, per molecule, at least two C 2 -C 6 alkenyl radicals bonded to silicon atoms and, preferably, chosen from organopolysiloxane compounds containing units of formula (V):
• radicals Z which may be identical or different, represent a linear or branched alkenyl radical having from 2 to 6 carbon atoms;
• radicals U which are identical or different, represent a hydrocarbon radical having from 1 to 12 carbon atoms
• At least one organohydrogenpolysiloxane compound B comprising, per molecule, at least two hydrogen atoms, preferably at least three, bonded to an identical or different silicon atom, and
• nanoparticles or a colloidal suspension comprising nanoparticles as defined above are examples of nanoparticles or a colloidal suspension comprising nanoparticles as defined above.
• the composition X according to the invention is a crosslinkable composition, in which the compound B is chosen from organopolysiloxanes comprising at least one unit of formula (VIII):
• radicals U which are identical or different, represent a hydrocarbon radical having from 1 to 12 carbon atoms
• the molar concentration of metal, originating from the nanoparticles, of the composition X according to the invention is between 0.01% and 15%, preferably between 0.05% and 10%, and even more preferentially between 0.1% and 4% relative to the number of total moles of unsaturations carried by the unsaturated compound A.
• the composition X according to the invention is free of platinum, palladium, ruthenium or rhodium-based catalyst.
• free of catalyst is meant that the composition X according to the invention comprises less than 1 % by weight of catalyst based on platinum, palladium, ruthenium or rhodium, preferably less than 10 -2% by weight. weight, and more preferably less than 10 -3% by weight, relative to the total weight of the composition.
• the composition X according to the invention also comprises one or more functional additives that are customary in silicone compositions.
• functional additives that are customary in silicone compositions.
• families of usual functional additives mention may be made of: - the charges ;
• additives for heat resistance, resistance to oils or fire resistance for example metal oxides.
• compositions X according to the invention can in particular be obtained by firstly introducing, under an inert atmosphere, the nanoparticles or the colloidal suspension comprising nanoparticles in the reaction medium, and then adding compound A with stirring. Finally, compound B is introduced and, if necessary, the temperature of the mixture is increased to reach the reaction temperature.
• the invention also relates to a crosslinked silicone material Y obtained by heating at a temperature ranging from 15 ° C. to 150 ° C., a crosslinkable composition X comprising:
• At least one unsaturated compound A comprising, per molecule, at least two C 2 -C 6 alkenyl radicals bonded to silicon atoms and chosen from organopolysiloxane compounds comprising units of formula (V):
• radicals Z which are identical or different, represent a linear or branched alkenyl or alkynyl radical having from 2 to 6 carbon atoms;
• radicals U which are identical or different, represent a hydrocarbon radical having from 1 to 12 carbon atoms,
• At least one organohydrogenpolysiloxane compound B comprising, per molecule, at least two hydrogen atoms bonded to an identical or different silicon atom, and
• nanoparticles or a colloidal suspension comprising nanoparticles as defined above are examples of nanoparticles or a colloidal suspension comprising nanoparticles as defined above.
• the present invention is illustrated in more detail in the nonlimiting exemplary embodiments.
• FIG. 1A represents a photo of STEM HAADF of the colloidal solution comprising iron nanoparticles.
• Figure 1B shows the number of nanoparticles as a function of their diameter. The average diameter of the nanoparticles is 2.6 nm ⁇ 0.7 nm.
• the iron nanoparticles impregnated on Si0 2 were analyzed by infrared spectroscopy and compared to the precursor used (Fe 3 (CO) i 2 ).
• Figure 2 shows the results obtained. These results show that there is no more precursor present in the nanoparticles and that carbonyl ligands are well coordinated to the iron nanoparticles. Moreover, the peaks between 2800 and 3000 cm 1 demonstrate the presence of at least one silicide on the nanoparticles.
• the nanoparticles have also been characterized by NMR.
• Figure 3 shows the spectrum
• the nanoparticles have also been characterized by Môssbauer spectroscopy.
• Figure 9 shows the Mössbauer spectrum obtained. This spectrum shows that the nanoparticles obtained comprise iron at oxidation state 0, at least one silicide and that they have no magnetic contribution, they are therefore not paramagnetic.
• the above procedure was also used to synthesize nanoparticles by varying the temperature and the iron precursor (see Table 1).
• Iron nanoparticles not comprising a carbonyl ligand have also been synthesized. These nanoparticles were synthesized according to the above procedure at 120 ° C., from Fe (C 8 H 8 ) 2 and under 3 bar CO. Despite the CO atmosphere, the nanoparticles obtained do not include a carbonyl ligand.
• Iron nanoparticles were also synthesized according to the procedure of Example 1 at 140 ° C.
• the iron nanoparticles impregnated on SiO 2 were analyzed by infrared spectroscopy. The spectrum obtained shows that the iron nanoparticles prepared at 140 ° C. do not include a carbonyl ligand.
• FIG. 5A represents a STEM HAADF photo of the colloidal solution comprising cobalt nanoparticles.
• Figure 5B shows the number of nanoparticles as a function of their diameter.
• the average diameter of the nanoparticles is 1.6 nm ⁇ 0.3 nm.
• Figure 4 shows the 1H-NMR spectrum of cobalt nanoparticles and n-octylsilane. These results show that n-octylsilane reacts well with Co 2 (CO) 8 because the peak at 3.6 ppm is no longer visible.

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