Hydrosilylation process catalysed by a manganese complex

Abstract

The present invention relates to hydrosilylation reactions between a monosubstituted alkene compound and a compound comprising at least one hydrogen atom bonded to a silicon atom. More specifically, the invention relates to a process for hydrosilylation of an unsaturated compound A comprising at least one monosubstituted alkene function with a compound B comprising at least one hydrosilyl function, catalysed by a manganese complex C having the oxidation state I, in the presence of air and / or water. This hydrosilylation reaction between an alkene compound and a compound comprising at least one hydrogen atom bonded to a silicon atom makes it possible in particular to crosslink silicone compositions.

Description

[0001] DESCRIPTION

[0002] TITLE: Manganese complex-catalyzed hydrosilylation process

[0003] Technical field

[0004] The present invention relates to hydrosilylation reactions between a monosubstituted alkene compound and a compound comprising at least one hydrogen atom bonded to a silicon atom. More specifically, the invention relates to a hydrosilylation process catalyzed by a manganese complex. This hydrosilylation reaction between an alkene compound and a compound comprising at least one hydrogen atom bonded to a silicon atom allows in particular the crosslinking of silicone compositions.

[0005] State of the prior art

[0006] In a hydrosilylation reaction of alkene compounds (also called polyaddition), a compound comprising at least one double bond reacts with a compound comprising at least one hydrogenosilyk function, i.e. a hydrogen atom bonded to a silicon atom. This reaction can for example be described by:

[0007] The hydrosilylation reaction can be accompanied by, or sometimes even replaced by, a dehydrogenative silylation reaction (also called dehydrosilylation). The reaction can be described by:

[0008] The hydrosilylation reaction is notably used to crosslink silicone compositions comprising organopolysiloxanes bearing alkenyl units and organopolysiloxanes comprising hydrogenosilyl functions.

[0009] The hydrosilylation reaction of alkene compounds is typically carried out by catalysis, using metal or organometallic catalysts. Currently, the suitable catalyst for this reaction is a platinum catalyst. Thus, most industrial hydrosilylation processes, particularly of alkenes, are catalyzed by Speier hexachloroplatinic acid or by the Karstedt Pt(O) complex of general formula Pt2(divinyltetramethyldisiloxane)3 (or abbreviated Pt2(DVTMS)3). In the early 2000s, the preparation of platinum-carbene complexes provided access to more stable catalysts (see for example patent application WO 01 / 42258).

[0010] However, the use of platinum-based metal or organometallic catalysts is still problematic. It is an expensive metal, becoming increasingly rare, and its cost fluctuates enormously. Its use on an industrial scale is therefore difficult. The aim is therefore to reduce the amount of catalyst required for the reaction as much as possible, without reducing the yield and speed of the reaction. Many studies have been conducted to find alternatives to the Karstedt catalyst.

[0011] Over the past decade, the use of homogeneous manganese-based catalysts in organic synthesis has been described as a possible alternative. The scientific article by Antonio Torres-Calis and Juventino J. Garni entitled "Homogeneous Manganese-Catalyzed Hydrofunctionalizations of Alkenes and Alkynes: Catalytic and Mechanistic Tendencies" (ACS Omega 2022, 7, 37008-37038) provides a comprehensive review of manganese-based catalytic systems proposed, particularly for the hydrosilylation of alkenes. The scientific article by Dong et al, "Manganese-Catalyzed divergent silylation of alkenes" (Nature Chemistry, vol. 13, Feb 2021, 182-190) describes a manganese-based catalyst for the dehydrosilylation and hydrosilylation of alkenes. Mn2(CO)io is used as a metal precursor and must be associated with a ligand, preferably a JackiePhos ligand to promote the hydrosilylation reaction. In the Mn2(CO)io complex, manganese is in oxidation state 0.

[0012] Yang X. and Wang C. (“Diverse Fates of -silyl Radical under Mangenese Catalysis: Hydrosilylation and Desydrogenative Silylation of Alkenes” Chin. J. Chem. 2018, 36, 1047-1051) described the chemoselective and regioselective hydrosilylation of alkenes catalyzed by the MnBr(CO)5 complex. The authors proved the radical nature of the reaction mechanism. The hydrosilylation process was carried out under an inert atmosphere, protected from air and water. All examples were carried out under an inert atmosphere in dry Schlenk tubes. The solvents were purified by distillation over sodium and stored under nitrogen.

[0013] More recently, a scientific article (Anthony Vivien, Laurent Veyre, Raphaël Mirgalet, Clément Camp, Chloé Thieuleux, “Mn2(CO)io and UV light: a promising combination for regioselective alkene hydrosilylation at low temperature”, Chem. Commun., 2022,58, 4091-4094) described the use of another manganese-based catalyst: dimanganese decacarbonyl, with the chemical formula [Mn2(CO)io]. Advantageously, it is a commercial product, inexpensive and stable in air. However, the hydrosilylation reaction itself is always carried out under an inert atmosphere, in dry flasks under argon. The reagents and solvents were purified and stored under argon in glove boxes.

[0014] Due to the radical mechanism of the reaction, there is a technical prejudice that the catalysts described in the prior art must be used in anhydrous conditions, protected from air and water. In addition, other reagents and any solvents must be purified and dried before use. From an industrial point of view, it is difficult and expensive to meet such conditions.

[0015] It is in this context that the inventors sought a more efficient process for the hydrosilylation of alkene compounds. Advantageously, it is desired to overcome the constraints linked to the sensitivity of the reaction to air and humidity. In addition, it is desired that the hydrosilylation reaction be rapid, at moderate temperature, and selective, in particular that the dehydrosilylation and / or isomerization reactions of the alkene compound be reduced or even negligible. Finally, it is desired that the catalyst contain an abundant, inexpensive and non-toxic chemical element.

[0016] Summary of the invention

[0017] Against all expectations, the inventors discovered that catalysts based on manganese in oxidation state I could advantageously be used in the presence of water and air. The inventors discovered that the hydrosilylation reaction of monosubstituted alkenes could be catalyzed by manganese complexes in oxidation state I, with excellent yields and excellent selectivity, under conditions close to industrial conditions, in air and with unpurified reagents.

[0018] The subject of the present invention is a process for the hydrosilylation of an unsaturated compound A comprising at least one monosubstituted achene function, with a compound B comprising at least one hydrogenosilyl function, catalyzed by a manganese complex with oxidation state IC, in the presence of air and / or water.

[0019] Brief description of the figures

[0020] Figure 1 illustrates comparative example 1.

[0021] Detailed description of the invention

[0022] Unless otherwise stated, all viscosities of silicone oils referred to in this document 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.

[0023] Although not drawn, possible tautomeric forms of the compounds described herein are included within the scope of the present invention. In the present invention, an alkyl group may be linear or branched. An alkyl group preferably comprises between 1 and 30 carbon atoms, more preferably between 1 and 12 carbon atoms, even more preferably between 1 and 6 carbon atoms. An alkyl group may for example be selected from the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.

[0024] In the present invention, a cycloalkyl group may be monocyclic or polycyclic, preferably monocyclic or bicyclic. A cycloalkyl group preferably comprises between 3 and 30 carbon atoms, more preferably between 3 and 8 carbon atoms. A cycloalkyl group may for example be chosen from the following groups: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantane and norborane.

[0025] In the present invention, an aryl group may be monocyclic or polycyclic, preferably monocyclic, and preferably comprises between 6 and 30 carbon atoms, more preferably between 6 and 18 carbon atoms. An aryl group may be unsubstituted or substituted one or more times by an alkyl group. The aryl group may be selected from phenyl, naphthyl, anthracenyl, phenanthryl, mesityl, tolyl, xylyl, diisoproylphenyl and triisopropylphenyl groups.

[0026] In the present invention, an aryl-alkyl group preferably comprises between 6 and 30 carbon atoms, more preferably between 7 and 20 carbon atoms. An aryl-alkyl group may for example be chosen from the following groups: benzyl, phenylethyl, phenylpropyl, naphylmethyl, naphthylethyl and naphthylpropyl.

[0027] In the present invention, the halogen atom may for example be selected from the group consisting of fluorine, bromine, chlorine and iodine, with fluorine being preferred. A fluorine-substituted alkyl group may for example be trifluoropropyl.

[0028] The present invention uses a catalyst C consisting of a manganese (I) complex, i.e. in oxidation state I. Advantageously, manganese is an abundant natural element and generally considered non-toxic within the limits of the doses which make it a trace element. In the present invention, the manganese (I) complex is a metal complex consisting of one or more manganese atoms in oxidation state I and ligands linked to the manganese.

[0029] The manganese(I) complex according to the invention may be a metal complex consisting of one or more manganese atoms in oxidation state I, carbonyl ligands, and a type X ligand bound to the manganese. By definition, a type X ligand contributes only one electron to the coordination sphere of the metal to which it is bound.

[0030] According to one embodiment, the manganese (I) complex may be chosen from complexes of formula Mn(CO)sZ, in which Z represents a coordinating or non-coordinating anion. Z may for example be chosen from the group consisting of: H", F", CF, Br", F, OH", BF4", PF6", NOC. CIO / . RCOCT, CF3COO", RSO3", BH4", BR4", A1R4; A1(OR)4', NH2“, RCT, CN“, R2N“ SCN“, OCN“, OCP' , RS“, R'CONFT, (R-CO)2N“, HCOL. HSO4“, H2PO4“, acetylacetonate, pentafluorobenzoate, bis(trimethylsilyl)amide, tetrakis[pentafluorophenyl]borate and tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, R representing a CHO, CF3, C2F5, C(CF3)3 alkyl group, a C3-10 cycloalkyl group, a C3-10 heterocyclic group comprising at least one N, O or S heteroatom, a C10 aryl group, or a C5-10 heteroaryl group comprising at least one N, O or S heteroatom.

[0031] Most preferably, the manganese(I) complex is specifically manganese(I) bromo-pentacarbonyl, of chemical formula [MnBr(CO)5] (CAS Number: 14516-54-2). Advantageously, it is a commercial product, inexpensive and stable in air.

[0032] Catalyst C according to the invention is advantageously used without organic ligand, in particular:

[0033] - without a nitrogen-based ligand, such as for example a pyridine ligand, and / or

[0034] - without a phosphorus-based ligand, such as for example a phosphine ligand, and / or

[0035] - without acyl ligand, and / or

[0036] - without a diketone ligand, such as for example a p-diketone ligand, and / or

[0037] - without cyclopentadienyl ligand, substituted or unsubstituted, and / or

[0038] - without organometallic ligand, such as triphenylarsine.

[0039] The molar concentration of catalyst C may be from 0.01 mol.% to 15 mol.%, more preferably from 0.05 mol.% to 10 mol.%, more preferably from 0.1 mol.% to 5 mol.%, even more preferably from 0.2 mol.% to 2 mol.%, relative to the total number of moles of unsaturations carried by the unsaturated compound A.

[0040] According to a preferred variant, in the process according to the invention, no compounds based on platinum, palladium, ruthenium or rhodium are used. The quantity of compounds based on platinum, palladium, ruthenium or rhodium in the reaction medium is, for example, less than 0.1% by weight relative to the weight of catalyst C, preferably less than 0.01% by weight, and more preferably less than 0.001% by weight.

[0041] In the hydrosilylation process according to the present invention, the unsaturated compound A used comprises at least one monosubstituted alkene function. Said monosubstituted alkene unsaturation is not part of an aromatic cycle. The unsaturated compound A may be chosen from those known to those skilled in the art and which do not contain a reactive chemical function which could hinder or even prevent the hydrosilylation reaction.

[0042] In this text, the term "monosubstituted achene" or "monosubstituted alkenyl" means a covalent double bond between two carbon atoms, not forming part of an aromatic cycle, the two carbon atoms being linked to 3 hydrogen atoms and a monovalent radical different from the hydrogen atom. The unsaturated compound A used in the hydrosilylation process according to the invention can be represented by the general formula (1): RCH=CH2(1) in which R represents a monovalent radical.

[0043] According to one embodiment, the unsaturated compound A comprises one or more monosubstituted alkene functions and from 2 to 40 carbon atoms. The unsaturated compound A can be represented by the general formula (1): RCH=CH2(1) in which R represents a monovalent radical chosen from the group consisting of:

[0044] - an alkyl group having between 1 and 30 carbon atoms, more preferably between 1 and 12 carbon atoms, even more preferably between 1 and 6 carbon atoms, optionally substituted by one or more halogen atoms such as chlorine or fluorine, and optionally by one or more groups chosen from -OH and -OSiR's, in which each R' represents, independently of one another, H or an alkyl group;

[0045] - an aryl group having between 6 and 30 carbon atoms, more preferably between 6 and 18 carbon atoms, optionally substituted by one or more halogen atoms such as chlorine or fluorine, and optionally by one or more groups chosen from alkyl groups, haloalkyl groups, -OH, -OR' and -OSiR's, in which each R' represents, independently of one another, H or an alkyl group;

[0046] - an aryl-alkyl group preferably comprises between 6 and 30 carbon atoms, more preferably between 7 and 20 carbon atoms, optionally substituted on its aryl part and / or on its alkyl part by one or more halogen atoms such as chlorine or fluorine, and optionally by one or more groups chosen from alkyl groups, haloalkyl groups, -OH, -OR' and -OSiR's, in which each R' represents, independently of one another, H or an alkyl group;

[0047] - an ether group of formula -LOR”, in which L represents a bond or a divalent radical, preferably an alkylene group having from 1 to 12 carbon atoms, even more preferably between 1 and 6 carbon atoms, and R' ' represents a group chosen from: an alkyl group having between 1 and 30 carbon atoms, more preferably between 1 and 12 carbon atoms, even more preferably between 1 and 6 carbon atoms, optionally substituted by one or more halogen atoms such as chlorine or fluorine, and optionally by one or more groups chosen from -OH and -OSiR's, in which each R' represents, independently of one another, H or an alkyl group;an aryl group having between 6 and 30 carbon atoms, more preferably between 6 and 18 carbon atoms, optionally substituted by one or more halogen atoms such as chlorine or fluorine, and optionally by one or more groups chosen from alkyl groups, haloalkyl groups, -OH, -OR' and -OSiR's, in which each R' represents, independently of one another, H or an alkyl group; and an aryl-alkyl group preferably comprises between 6 and 30 carbon atoms, more preferably between 7 and 20 carbon atoms, optionally substituted on its aryl part and / or on its alkyl part by one or more halogen atoms such as chlorine or fluorine, and optionally by one or more groups chosen from alkyl groups, haloalkyl groups, -OH, -OR' and -OSiR'3, in which each R' represents, independently of one another, H or an alkyl group;

[0048] - an ester group of formula -LC(O)-OR” or -LOC(O)-R”, in which L and R” have the same definitions as those given above.

[0049] The unsaturated compound A may, preferably, be an organic compound comprising a monosubstituted alkene group chosen from the group consisting of:

[0050] - α-olefins, preferably 1-octene and 1-hexene,

[0051] - chlorinated a-olefins, preferably allyl chloride,

[0052] - fluorinated a-olefins, preferably 4,4,5,5,6,6,7,7,7-nonafluoro-l-heptene,

[0053] - allyl alcohol,

[0054] - allyl ethers, such as allyl benzyl ether, allyl phenyl ether, allyl C 1 -C 8 alkyl ethers, allyl glycidyl ether, allyl piperidine ether, preferably sterically hindered allyl piperidine ether, allyl silyl ethers, preferably trimethylsilyl allyl ether,

[0055] - aliphatic alkenoic acid esters, such as C1-C4 alkyl acrylates,

[0056] - acrylic acid,

[0057] - allyl esters, such as allyl acetate,

[0058] - styrenes, allylbenzenes, and phenylated α-olefins,

[0059] - 1,2-epoxy-4-vinylcyclohexane.

[0060] The unsaturated compound A may be a disiloxane, such as vinyl pentamethyl disiloxane and divinyl tetramethyl disiloxane.

[0061] The unsaturated compound A may be chosen from compounds comprising several monosubstituted alkene functions, preferably two or three monosubstituted achene functions, and particularly preferably, the compound A is chosen from the following compounds:

[0062] According to a particularly preferred embodiment, the unsaturated compound A may be an organopolysiloxane compound comprising one or more monosubstituted alkene functions, preferably at least two monosubstituted alkene functions. The hydrosilylation reaction of alkenes is one of the key reactions in silicone chemistry. It allows not only the crosslinking between organopolysiloxanes with SiH functions and organopolysiloxanes with alkenyl functions to form networks and provide mechanical properties to the materials, but also the functionalization of organopolysiloxanes with SiH functions to modify their physical and chemical properties.

[0063] Said organopolysiloxane compound can in particular be formed:

[0064] - at least two siloxyl units of the following formula: Y a R 1 b SiO(4- a -b) / 2 in which:

[0065] Y is a C2-C12 monosubstituted alkenyl group, preferably vinyl,

[0066] R 1 is a monovalent hydrocarbon group having from 1 to 12 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, and a=1, 2 or 3, preferably a=1 or 2, more preferably a=1; b=0, 1 or 2; and the sum a+b=1, 2 or 3; and

[0067] - possibly patterns of the following formula: R 1 c SiO(4- C ) / 2 in which R 1 has the same meaning as above and c = 0, 1, 2 or 3.

[0068] It is understood in the above formulas that, if several R groups 1 are present or if several Y groups are present, they can be identical or different from each other. Preferably R1 may represent a monovalent radical selected 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 3 to 8 carbon atoms and aryl groups having 6 to 12 carbon atoms. R 1 may advantageously be selected from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyk, xylyk, tolyk and phenyl.

[0069] These organopolysiloxane compounds comprising one or more monosubstituted achene functions may have a linear structure, a cyclic structure or a branched structure.

[0070] In the following section concerning the description of unsaturated organopolysiloxane, the following nomenclature has been used to represent the siloxyl units: - a siloxyl unit "M V1 » represents a siloxyl unit of formula

[0071] - a siloxyl unit “M” represents a siloxyl unit of formula R

[0072] - a siloxyl motif “D V1 » represents a siloxyl unit of formula

[0073] - a siloxyl unit “D” represents a siloxyl unit of formula R

[0074] - a siloxyl unit “T” represents a siloxyl unit of formula R 1 SiOs / 2,

[0075] - a siloxyl unit “Q” represents a siloxyl unit of formula SiOjn- the symbols Y and R 1 being as described above.

[0076] As examples of “M” and “M V1 » terminals, we can cite the trimethylsiloxy, dimethylphenylsiloxy, dimethylvinylsiloxy or dimethylhexenylsiloxy groups.

[0077] As examples of patterns "D" and "D V1", we can cite the dimethylsiloxy, methylphenylsiloxy, methylvinylsiloxy, methylbutenylsiloxy, methylhexenylsiloxy, methyldecenylsiloxy or methyldecadienylsiloxy groups.

[0078] Linear organopolysiloxane compounds comprising one or more monosubstituted alkene functions are essentially composed of siloxyl units “D” and “D V1 » and siloxyl motifs “M” and “M V1 ». Examples of linear organopolysiloxanes which may be organopolysiloxane compounds comprising one or more monosubstituted alkene functions according to the invention are:

[0079] - a poly(dimethylsiloxane) with dimethylvinylsilyl ends;

[0080] - a poly(dimethylsiloxane-co-methylphenylsiloxane) with dimethyl-vinylsilyl ends;

[0081] - a poly(dimethylsiloxane-co-methylvinylsiloxane) with dimethyl-vinylsilyl ends; and

[0082] - a poly(dimethylsiloxane-co-methylvinylsiloxane) with trimethylsilyl ends.

[0083] In the most preferred form, the organopolysiloxane compound comprising one or more monosubstituted alkene functions contains terminal dimethylvinylsilyl units. Even more preferably, the organopolysiloxane compound comprising one or more monosubstituted alkene functions is a poly(dimethylsiloxane) with dimethylvinylsilyl ends.

[0084] A silicone oil generally has a viscosity of between 1 mPa.s and 2,000,000 mPa.s. Preferably, said organopolysiloxane compounds comprising one or more alkene functions are silicone oils with a dynamic viscosity of between 20 mPa.s and 100,000 mPa.s, preferably between 20 mPa.s and 80,000 mPa.s at 25°C, and more preferably between 100 mPa.s and 50,000 mPa.s.

[0085] Cyclic organopolysiloxane compounds comprising one or more monosubstituted alkene functions are essentially composed of siloxyl units “D” and “D V1 » as described above. An example of a cyclic organopolysiloxane that may be an organopolysiloxane compound comprising one or more monosubstituted alkene functions according to the invention is cyclic poly(methylvinylsiloxane). Optionally, the organopolysiloxane compounds comprising one or more monosubstituted alkene functions may further contain “T” siloxyl units and / or “Q” siloxyl units. The organopolysiloxane compounds comprising one or more monosubstituted alkene functions then have a branched structure. Examples of branched organopolysiloxanes, also called resins, that may be organopolysiloxane compounds comprising one or more monosubstituted alkene functions according to the invention are:

[0086] - MD V1Q, where vinyl groups are included in the D units,

[0087] - MD V1 TQ, where vinyl groups are included in D motifs,

[0088] - MM V1 Q, where vinyl groups are included in part of the M units,

[0089] - MM V1 TQ, where vinyl groups are included in part of the M motifs,

[0090] - MM V1 DD V1 Q, where vinyl groups are included in part of the M and D units,

[0091] - and their mixtures.

[0092] Preferably, the organopolysiloxane compound comprising one or more monosubstituted alkene functions has a mass content of monosubstituted alkenyl unit of between 0.001% and 30%, preferably between 0.01% and 10%, preferably between 0.02 and 5%.

[0093] The unsaturated compound A reacts according to the present invention with a compound B comprising at least one hydrogenosilyl function.

[0094] According to one embodiment, compound B comprising at least one hydrogenosilyl function is a silane or polysilane compound comprising at least one hydrogen atom bonded to a silicon atom. By “silane” compound is meant in the present invention chemical compounds comprising a silicon atom bonded to four hydrogen atoms or to organic substituents. By “polysilane” compound is meant in the present invention chemical compounds having at least one =Si-Si= unit. Among the silane compounds, compound B comprising at least one hydrogenosilyl function may be a mono-, di- or tri-alkylsilane or a mono-, di- or tri-arylsilane, for example triethylsilane, phenyldimethylsilane, benzyldimethylsilane, and diphenylsilane.

[0095] According to another embodiment, compound B comprising at least one hydrogenosilyl function is an organopolysiloxane compound comprising at least one hydrogen atom bonded to a silicon atom, also called organohydrogenpolysiloxane. Said organohydrogenpolysiloxane may advantageously be an organopolysiloxane formed:

[0096] - at least two siloxyl units of the following formula: H d R 2 e SiO(4-de) / 2 in which:

[0097] R 2is a monovalent hydrocarbon group having from 1 to 12 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 d=1, 2 or 3, preferably d=1 or 2, more preferably d=1; 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.

[0098] It is understood in the above formulas that, if several R groups 2 are present, they can be identical or different from each other. Preferably R 2may represent a monovalent radical selected 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 3 to 8 carbon atoms and aryl groups having 6 to 12 carbon atoms. R 2 may advantageously be selected from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl.

[0099] The organohydrogenpolysiloxane 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.

[0100] In the following section regarding the description of organohydrogenpolysiloxane, the following nomenclature has been used to represent the siloxyl units:

[0101] - a siloxyl unit “M” represents a siloxyl unit of formula R 2 3SiOi / 2,

[0102] - a siloxyl unit “M'” represents a siloxyl unit of formula HR 2 2SiOi / 2,

[0103] - a siloxyl unit “D” represents a siloxyl unit of formula R 2 2SiO2 / 2,

[0104] - a siloxyl unit “D'” represents a siloxyl unit of formula HR 2 SiC>2 / 2,

[0105] - a siloxyl unit “T” represents a siloxyl unit of formula R 2 SiO 5 / 2.

[0106] - a siloxyl unit “Q” represents a siloxyl unit of formula SiCL”. the symbol R 1 being as described above.

[0107] When linear polymers are concerned, these essentially consist of siloxyl units chosen from the siloxyl units “D” and “D'”, and of terminal siloxyl units “M” and “M'”. Examples of organohydrogenpolysiloxanes which may be compounds B comprising at least one hydrogenosilyl function according to the invention are:

[0108] - a poly(dimethylsiloxane) with hydrogenodimethylsilyl ends;

[0109] - a poly(dimethylsiloxane-co-methylhydrogensiloxane) with trimethylsilyl ends;

[0110] - a poly(dimethylsiloxane-co-methylhydrogensiloxane) with hydrogen-dimethylsilyl ends; and

[0111] - a poly(methylhydrogensiloxane) with trimethylsilyl ends.

[0112] When the organohydrogenpolysiloxane has a cyclic structure, it is essentially composed of siloxyl units chosen from the siloxyl units “D” and “D'”. An example of a cyclic organohydrogenpolysiloxane which may be a compound B comprising at least one hydrogenosilyl function according to the invention is a cyclic poly(methylhydrogensiloxane).

[0113] When the organohydrogenopolysiloxane has a branched structure, it is preferably chosen from the group consisting of silicone resins of the following formulae: - M'Q where the hydrogen atoms linked to silicon atoms are carried by the groups M,

[0114] - MM'Q where the hydrogen atoms linked to silicon atoms are carried by a part of the M patterns,

[0115] - MD'Q where the hydrogen atoms linked to silicon atoms are carried by the D groups,

[0116] - MDD'Q where the hydrogen atoms linked to silicon atoms are carried by part of the D groups,

[0117] - MM'TQ where the hydrogen atoms linked to silicon atoms are carried by part of the M motifs,

[0118] - MM'DD'Q where the hydrogen atoms linked to silicon atoms are carried by part of the M and D motifs,

[0119] - and their mixtures.

[0120] Preferably, the organohydrogenpolysiloxane compound 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%.

[0121] The amounts of compound A and compound B may be controlled so that the molar ratio of the hydrogenosilyl functions of compounds B to the monosubstituted alkene functions of compounds A is preferably between 1:10 and 10:1, more preferably between 1:5 and 5:1, more preferably between 1:3 and 3:1, and even more preferably between 1:2 and 2:1.

[0122] According to a particular embodiment of the present invention, it is possible that the unsaturated compound A and the compound B comprising at least one hydrogenosilyl function are one and the same compound, comprising on the one hand at least one mono-substituted alkene function, and on the other hand at least one silicon atom and at least one hydrogen atom bonded to the silicon atom. This compound can then be described as "bifunctional", and it is capable of reacting with itself by hydrosilylation reaction. The invention can therefore also relate to a process for hydrosilylation of a bifunctional compound with itself, said bifunctional compound comprising on the one hand at least one mono-substituted achene 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 catalyzed by catalyst C as described above.

[0123] Examples of organopolysiloxanes that can be bifunctional compounds are:

[0124] - a poly(dimethylsiloxane-co-hydrogenomethylsiloxane-co-vinylmethyl-siloxanes) with dimethylvinylsilyl ends;

[0125] - a poly(dimethylsiloxane-co-hydrogenomethylsiloxane-co-vinylmethyl-siloxanes) with dimethylhydrogenosilyl ends; and

[0126] - a poly(dimethylsiloxane-co-hydrogenomethylsiloxane-co-propylglycidylethermethylsiloxane) with trimethylsilyl ends. When it comes to the use of the unsaturated compound A and the compound B comprising at least one hydrogenosilyl function, the person skilled in the art understands that this also means the use of a bifunctional compound.

[0127] The process according to the present invention is characterized in particular by the fact that the hydrosilylation reaction is carried out in the presence of air and / or water. Indeed, it has been discovered, very surprisingly, that the reaction is not very sensitive to air and humidity.

[0128] The hydrosilylation process according to the invention is preferably carried out in air; it is not carried out under an inert atmosphere, in particular it is not carried out under nitrogen, under argon or under oxygen-depleted air.

[0129] The hydrosilylation reaction can be carried out at a temperature between 15°C and 300°C, preferably between 20°C and 240°C, more preferably between 50°C and 200°C, more preferably between 50°C and 140°C, and even more preferably between 50°C and 100°C.

[0130] The hydrosilylation reaction can be carried out in a solvent or in the absence of a solvent. Suitable solvents are solvents miscible with compound B. For example, the solvent can be selected from the group consisting of aliphatic hydrocarbons, such as pentane, hexane, heptane, cyclohexane, decalin, and paraffin oils; aromatic hydrocarbons, such as toluene, and xylene; mixtures of hydrocarbons of mineral or synthetic origin, such as white spirit; ethers, such as tetrahydrofuran, dioxane, diethyl ether, diphenyl ether, and anisole; chlorinated hydrocarbons, such as methylene chloride, 1,2-dichloroethane, perchloroethylene, and chlorobenzene; esters, such as ethyl acetate, butyl acetate, and butyrolactone; acetonitrile; dimethylformamide; dimethyl sulfoxide; N-methylpyrrolidone; polyethylene glycols; water; and mixtures thereof.Preferably, the solvent may be chosen from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons and chlorinated hydrocarbons, and more preferably from the group consisting of hexane, cyclohexane, decalin, and toluene.

[0131] Alternatively, the solvent may be chosen from volatile silicones, octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), polydimethylsiloxane oils (PDMS), polyphenylmethylsiloxane oils (PPMS) or mixtures thereof. Alternatively, one of the reactants, for example the unsaturated compound A, may act as a solvent. Preferably, the use of organic solvents that are harmful to the environment and the health of workers in the manufacturing workshops will be avoided.

[0132] According to another variant, the solvent may be chosen from the most environmentally friendly solvents. For example, reference may be made to the scientific publications of Aider et al. (Green Chem., 2016, 18, 3879) or Prat et al. (Green Chem., 2016, 18, 288). Preferably, the solvent may be chosen from the group consisting of water, anisole and ethyl acetate, more preferably water and anisole.

[0133] When present, the amount of solvent may be adjusted by a person skilled in the art to ensure good miscibility of the reagents. For example, the volume of solvent may be between 5% and 70%, preferably between 10% and 50%, of the total volume of the reaction medium.

[0134] Advantageously, the reagents and solvents used in the process according to the invention can be used without a prior purification step. It has been found that, surprisingly, the performances of the hydrosilylation reaction obtained with unpurified reagents were equivalent to those obtained with purified reagents.

[0135] The discovery of this new hydrosilylation process according to the present invention makes it possible to envisage numerous applications.

[0136] When the compounds A and B used are chosen from organopolysiloxanes as defined above, the hydrosilylation reaction makes it possible to form a three-dimensional network, which leads to the curing or crosslinking of the composition. Crosslinking involves a progressive physical change in the medium constituting the composition. Consequently, the process according to the invention can be used to obtain elastomers, gels, foams, etc. In this case, a crosslinked silicone material is obtained. The term "crosslinked silicone material" means any silicone-based product obtained by crosslinking and / or curing of compositions comprising organopolysiloxanes having at least two unsaturated bonds and organopolysiloxanes having at least three hydrogenosilylated units. The crosslinked silicone material can, for example, be an elastomer, a gel or a foam.

[0137] According to this preferred embodiment of the process according to the invention, where compounds A and B are chosen from organopolysiloxanes as defined above, it is possible to use usual functional additives in silicone compositions. As families of usual functional additives, mention may be made of:

[0138] - the charges,

[0139] - adhesion promoters,

[0140] - inhibitors or retarders of the hydrosilylation reaction,

[0141] - adhesion modulators,

[0142] - silicone resins,

[0143] - additives to increase consistency,

[0144] - pigments (organic or mineral), and

[0145] - thermal resistance, oil resistance or fire resistance additives, for example metal oxides. Any filler provided is preferably mineral. The filler may be a very finely divided product with an average particle diameter of less than 0.1 μm. The filler may be siliceous in particular. In the case of siliceous materials, they may act as reinforcing or semi-reinforcing fillers. The reinforcing siliceous fillers are chosen from colloidal silicas, combustion and precipitation silica powders or mixtures thereof. These powders have an average particle size generally less than 0.1 μm (micrometers) and a BET specific surface area greater than 30 m 2 / g, preferably between 30 and 350 m 2 / g. Semi-reinforcing siliceous fillers such as diatomaceous earth or ground quartz may also be used. These silicas may be incorporated as such or after being treated with organosilicon compounds commonly used for this purpose. These compounds include methylpolysiloxanes such as hexamethyldisiloxane, octamethylcyclotetrasiloxane, methylpolysilazanes such as hexamethyldisilazane, hexamethylcyclotrisilazane, tetramethyldivinyldisilazane, chlorosilanes such as dimethyldichlorosilane, trimethylchlorosilane, methylvinyldichlorosilane, dimethylvinylchlorosilane, alkoxysilanes such as dimethyldimethoxysilane, dimethylvinylethoxysilane, trimethylmethoxysilane, and mixtures thereof. As for non-siliceous mineral materials, they can be used as semi-reinforcing or bulking mineral fillers.Examples of these non-siliceous fillers that can be used alone or in mixtures are calcium carbonate, possibly surface-treated with an organic acid or an ester of an organic acid, calcined clay, rutile-type titanium oxide, iron, zinc, chromium, zirconium, magnesium oxides, different forms of alumina (hydrated or not), boron nitride, lithopone, barium metaborate, barium sulfate and glass microbeads. These fillers are coarser, generally with an average particle diameter greater than 0.1 μm and a specific surface area generally less than 30 μm. 2 / g. These fillers may have been surface-modified by treatment with the various organosilicon compounds usually used for this purpose. Preferably, the filler is silica, and even more preferably combustion silica. Advantageously, the silica has a BET specific surface area of ​​between 75 m 2 / g and 410 m 2 / g. A silicone composition may comprise between 5% and 20% by weight of filler relative to the total weight of the silicone composition. Advantageously, the silicone composition may comprise between 8% and 15% by weight of filler.

[0146] According to a particularly preferred embodiment, the hydrosilylation process according to the present invention can be used for crosslinking between organopolysiloxanes with SiH functions and organopolysiloxanes with alkenyl functions, to form networks and provide mechanical properties to the materials. According to this embodiment, the unsaturated compound A comprising at least one monosubstituted alkene function is an organopolysiloxane compound comprising at least two monosubstituted alkene functions, and the compound B comprising at least one hydrogenosilyl function is an organopolysiloxane compound comprising at least three hydrogen atoms bonded to a silicon atom. A process for preparing crosslinked silicone materials can be described, characterized in that the crosslinking reaction between organopolysiloxanes with SiH functions and organopolysiloxanes with alkenyl functions is obtained by the hydrosilylation process as described above.The crosslinked silicone materials thus obtained can be used in different applications, including:

[0147] - “coating” type applications, where a support is covered with a silicone coating;

[0148] - applications in the field of electronics, for example for the preparation of conformal coatings for printed circuits, and for the filling (potting) of microcircuits and electronic components such as IGBTs;

[0149] - additive manufacturing processes (also known as 3D printing processes).

[0150] According to another embodiment, the hydrosilylation process according to the present invention can be used for the functionalization of organopolysiloxanes with SiH functions. The functionalization aims to modify the physical and / or chemical properties of said organopolysiloxanes, and to produce new compounds with improved properties. According to this embodiment, the unsaturated compound A comprising at least one monosubstituted alkene function is chosen from unsaturated compounds comprising one or more monosubstituted alkene functions and from 2 to 40 carbon atoms, and the compound B comprising at least one hydrogenosilk function is an organopolysiloxane compound comprising at least one hydrogen atom bonded to a silicon atom.A process for functionalizing organopolysiloxanes with SiH functions can be described, characterized in that the addition reaction between organopolysiloxanes with SiH functions and unsaturated compounds A comprising one or more monosubstituted achene functions and from 2 to 40 carbon atoms is obtained by the hydrosilylation process as described above.

[0151] Other details or advantages of the invention will appear more clearly from the examples given below for information purposes only.

[0152] The catalysts described in the prior art must be used under anhydrous conditions, protected from air and water. The sensitivity of Mn2(CO)io to air has been demonstrated in the following Comparative Example 1, illustrated by Figure 1:

[0153] Styrene and 1,1,1,3,5,5,5-heptamethyl-trisiloxane were introduced into a vial under argon atmosphere at room temperature. A solution of dimanganese decacarbonyl Mm / COjio in toluene was injected into the vial and toluene was added. Final concentration in Mm / COjio (relative to styrene) = 2 mol%. First, the reaction mixture was placed under UV light for 30 mm at room temperature. The reaction medium is clear pale yellow. After 30 minutes, the reaction medium was exposed to air. It is observed that the reaction medium very quickly becomes dark brown (see Figure 1) and the catalytic reaction stops.

[0154] Examples 1 and 2: Hydrosilylation of 1-octene (1) with LLL3,5.5.5-heptamethyl-trisiloxane (2)

[0155] Example 1: 1-Octene (1) (74 pL, 0.47 mmol) and 1,1,1,3,5,5,5-heptamethyl-trisiloxane (2)

[0156] (256 pL, 0.94 mmol) were introduced into a vial. A solution of MnBr(CO)s in toluene was injected into the vial and toluene was added. Final concentration of [Mu], relative to 1-octene = 2 mol%. Total volume of toluene = 195 pL. The reaction was carried out in air, without purification of the reagents and toluene.

[0157] After 4 h at 70°C, the reaction yield was 99%. No 1-octene isomerization products were detectable. No dehydrogenative silylation products were observed. The reaction is therefore selective for hydrosilylation.

[0158] Example 2: The same procedure described in Example 1 (70°C, 4h, in air without purification) was followed using a 1:1 molar ratio of 1-octene (1) (0.94 mmol) and 1,1,1,3,5,5,5-heptamethyl-trisiloxane (2) (0.94 mmol). After 4h at 70°C, the reaction yield was 96%. The isomerization rate of 1-octene was less than 1%. of different achenes

[0159] The same procedure described in Example 1 (70°C, 4 h, in air, in toluene, without purifications) was followed by varying the structure of the alkene compound (1') as indicated in Table 1 below. The quantities of reagents used were 1 eq. of alkene (1') for 1 or 2 eq. of heptamethyl-trisiloxane (2). The yield of hydrosilylation product (3') (determined by gas chromatography, calculated relative to the alkene) is indicated in Table 1. [Table 1]

[0160] In Examples 3 to 16, the hydrosilylation products were obtained with excellent selectivity. No C=C isomerization or C-O bond scission product was observed. On the other hand, the hydrosilylation product is not obtained from gem-disubstituted alkenes (Comparative Examples 2, 3 and 5) or from internal alkene (Comparative Example 4).

[0161] Examples 17-33: Hydrosilylation in different solvents

[0162] The same procedure described in Example 1 (70°C, 4 h, in air without purification) was followed by varying the nature of the solvent and the nature of the alkene, as indicated in Tables 2 and 3 below. The yield of hydrosilylation product (3) (determined by gas chromatography, calculated relative to the alkene) is indicated in Tables 2 and 3.

[0163] Alkene (1) = 1-octene. Molar ratio (1):(2) = 1:2 or 1:1.

[0164] [Table 2]

[0165] Different alkenes (1'). Molar ratio (l'):(2) = 1:1

[0166] [Table 3]

[0167] Examples 34-43: Hydrosilylation of different silanes

[0168] Styrene (0.47 mmol, 1 eq.) and a silane compound (0.94 mmol, 2 eq.) were introduced into a vial. A solution of MnBr(CO)s in anisole was injected into the vial and anisole was added. Final concentration of [Mn], relative to styrene = 2 mol%. The reaction was carried out in air at 70°C without purification of the reagents and anisole. After 4 h, the yield of hydrosilylation product (determined by gas chromatography, calculated relative to the alkene) is shown in Table 4.

[0169] [Table 4]

[0170] The same procedure described above for Examples 34-37 (70°C, 4h, in air without purification) was followed using a 1:1 molar ratio of different alkenes and different silanes. After 4h, the yield of hydrosilylation product (determined by gas chromatography, calculated relative to the alkene) is shown in Table 5. [Table 5]

[0171] Examples 34-43 show that MnBr(CO)s-catalyzed hydrosilylation works equally well with silane compounds and siloxane compounds (Examples 1-33). Examples 44-46: Effect of Reagent Purification

[0172] The same procedure described in Example 1 (70°C, 4h, in air) was followed except for the solvent: anisole was used instead of toluene. Different alkene compounds (1') were tested, with and without prior purification, as indicated in Table 6 below. The quantities of reagents used were 1 eq. of alkene (1') for 2 eq. of heptamethyl-trisiloxane (2). Final concentration in [Mu], relative to 1-octene = 2 mol%. The yield of hydrosilylation product (3') (determined by gas chromatography, calculated relative to the alkene) is indicated in Table 6.

[0173] [Table 6]

[0174] No significant difference could be observed between the use of a purified and an unpurified reagent in Examples 44 and 46. In Example 45, the slight decrease in yield can be explained by the presence of butylcatechol in the commercial styrene. Butylcatechol is a stabilizing agent that protects commercial styrene against free radical reactions. It is the cause of the decrease in catalytic activity during the hydrosilylation reaction.

[0175] Examples 47-49: Polysiloxane crosslinking reaction

[0176] The hydrosilylation reaction was carried out from a poly-methylhydrogen-siloxane oil of approximate structure MD' 50 M (Si-H unit content of approximately 45.5 wt.%).

[0177] Ex.47: Polymethylhydrogeno-siloxane oil (1 eq. of SiH functions) and divinyltetramethyldisiloxane (1 eq. of C=C functions) were mixed in a vial with 0.3 mol% of MnBr(CO)s, relative to the moles of SiH. The reaction was carried out in air, at 70°C, without prior purification. After 8 h, a gelling phenomenon was observed, which corresponds to the crosslinking of the composition.

[0178] Ex.48: Polymethylhydrogeno-siloxane oil (1 eq. of SiH functions) and diethyldiallylmalonate (1 eq. of C=C functions) were mixed in a vial with 0.3 mol% of MnBr(CO)s, relative to the moles of SiH. The reaction was carried out in air, at 70°C, without prior purification. After 2 h, a gelling phenomenon was observed, which corresponds to the crosslinking of the composition.

[0179] Ex.49: The unsaturated compound is an oil a, <n-divinylpolydiméthylsiloxane de structure approximative M V1 D64M V1(vinyl unit content of about 1 wt.%). The MnBr(CO)s catalyst was diluted in toluene, and mixed with a portion of the oil a, <n-divinylpolydiméthylsiloxane. Sous agitation, l’huile poly-méthyhydrogéno-siloxane et le reste de l’huile a,<n-divinylpolydiméthylsiloxane ont été ajoutés de façon à atteindre un ratio molaire SiH / SiVi de 1,7 et une teneur en MnBr(CO)s de 2% molaires, par rapport aux moles de SiH. La réaction a été conduite à 100°C à l’air. Au bout de 23 min, un gel a été obtenu dans tout le flacon.

[0180] Examples 50-56: Reaction with different functionalized alkenes

[0181] The hydrosilylation reaction was carried out from a poly-methylhydrogen-siloxane oil of approximate structure MD'soM (Si-H unit content of approximately 45.5 wt.%).

[0182] The same procedure described in Example 47 (70°C, in air, without purification) was followed by varying the alkene compound as indicated in Table 7 below. The gel time of the reaction media is indicated in Table 7. [Table 7]

[0183] Examples 50 to 56 indicate that the MnBr(CO)s catalyst not only catalyzes the hydrosilylation reaction between the hydrogenosilyl function and the C=C unsaturation, but also with the acetate groups (Ex. 50 and 51), acrylate groups (Ex. 52 and 53) and ketone groups (Ex. 54). In Examples 55 and 56, the crosslinking is obtained by opening the epoxide ring.

Claims

CLAIMS 1. Process for the hydrosilylation of an unsaturated compound A comprising at least one monosubstituted alkene function, with a compound B comprising at least one hydrogenosilyl function, catalyzed by a manganese complex with oxidation state IC, in the presence of air and / or water.

2. Hydrosilylation process according to claim 1, wherein the manganese complex in oxidation state I is chosen from complexes of formula Mn(CO)sZ, in which Z represents a coordinating or non-coordinating anion from the group consisting of: H", F", Cl", Br-, F, OH-, BF4“, PF6“, NOS-, Cio4RCOCT, CFsCOCr, RSO3“, BH4“, BR4“, A1R4-, A1(OR)4-, NH2-, RCT, CN“, R2N- SCN", OCN", OCP-, RS', R-CONH-, (R-CO)2N“, HCOF HSOF, H2PO4“, acetylacetonate, pentafluorobenzoate, bis(trimethylsilyl)amide, tetrakis[pentafluorophenyl]borate and tetrakis[3,5- bis(trifluoromethyl)phenyl] borate, R representing a Cno, CF3, C2F5, C(CF3)3 alkyl group, a C3-10 cycloalkyl group, a C3-10 heterocyclic group comprising at least one N, O or S heteroatom, a C5-10 aryl group, or a C5-10 heteroaryl group comprising at least one N, O or S heteroatom.

3. Hydrosilylation process according to claim 1 or claim 2, in which the manganese complex in oxidation state I is manganese (I) bromo-pentacarbonyl, of chemical formula [MnBr(CO)5].

4. Hydrosilylation process according to any one of claims 1 to 3, in which the unsaturated compound A comprises one or more monosubstituted alkene functions and from 2 to 40 carbon atoms, preferably the unsaturated compound A can be represented by the general formula (1): RCH=CH2(1) in which R represents a monovalent radical chosen from the group consisting of: - an alkyl group having between 1 and 30 carbon atoms, more preferably between 1 and 12 carbon atoms, even more preferably between 1 and 6 carbon atoms, optionally substituted by one or more halogen atoms such as chlorine or fluorine, and optionally by one or more groups chosen from -OH and -OSiR'3, in which each R' represents, independently of one another, H or an alkyl group; - an aryl group having between 6 and 30 carbon atoms, more preferably between 6 and 18 carbon atoms, optionally substituted by one or more halogen atoms such as chlorine or fluorine, and optionally by one or more groups chosen from alkyl groups, haloalkyl groups, -OH, -OR' and -OSiR'3, in which each R' represents, independently of one another, H or an alkyl group; - an aryl-alkyl group preferably comprises between 6 and 30 carbon atoms, more preferably between 7 and 20 carbon atoms, optionally substituted on its aryl part and / or on its alkyl part by one or more halogen atoms such as chlorine or fluorine, and optionally by one or more groups chosen from alkyl groups, haloalkyl groups, -OH, -OR' and -OSiR'3, in which each R' represents, independently of one another, H or an alkyl group; - an ether group of formula -LOR”, in which L represents a bond or a divalent radical, preferably an alkylene group having from 1 to 12 carbon atoms, even more preferably between 1 and 6 carbon atoms, and R' ' represents a group chosen from: an alkyl group having between 1 and 30 carbon atoms, more preferably between 1 and 12 carbon atoms, even more preferably between 1 and 6 carbon atoms, optionally substituted by one or more halogen atoms such as chlorine or fluorine, and optionally by one or more groups chosen from -OH and -OSiR'3, in which each R' represents, independently of one another, H or an alkyl group;an aryl group having between 6 and 30 carbon atoms, more preferably between 6 and 18 carbon atoms, optionally substituted by one or more halogen atoms such as chlorine or fluorine, and optionally by one or more groups chosen from alkyl groups, haloalkyl groups, -OH, -OR' and -OSiR'3, in which each R' represents, independently of one another, H or an alkyl group; and an aryl-alkyl group preferably comprises between 6 and 30 carbon atoms, more preferably between 7 and 20 carbon atoms, optionally substituted on its aryl part and / or on its alkyl part by one or more halogen atoms such as chlorine or fluorine, and optionally by one or more groups chosen from alkyl groups, haloalkyl groups, -OH, -OR' and -OSiR'3, in which each R' represents, independently of one another, H or an alkyl group; - an ester group of formula -LC(O)-O-R' ' or -LOC(O)-R' ' , in which L and R” have the same definitions as those given above.

5. Hydrosilylation process according to any one of claims 1 to 3, in which the unsaturated compound A is an organopolysiloxane compound comprising one or more monosubstituted alkene functions, preferably at least two monosubstituted alkene functions.

6. Hydrosilylation process according to any one of claims 1 to 5, in which compound B comprising at least one hydrogenosilyl function is an organopolysiloxane compound comprising at least one hydrogen atom bonded to a silicon atom.

7. Hydrosilylation process according to any one of claims 1 to 6, in which the hydrosilylation reaction is carried out in a solvent, said solvent preferably being chosen from: - the group consisting of aliphatic hydrocarbons, such as pentane, hexane, heptane, cyclohexane, decalin, and paraffin oils; aromatic hydrocarbons, such as toluene, and xylene; mixtures of hydrocarbons of mineral or synthetic origin, such as white spirit; ethers, such as tetrahydrofuran, dioxane, diethyl ether, diphenyl ether and anisole; chlorinated hydrocarbons, such as methylene chloride, 1,2-dichloroethane, perchloroethylene and chlorobenzene; esters, such as ethyl acetate, butyl acetate and butyrolactone; acetonitrile; dimethylformamide; dimethyl sulfoxide; N-methylpyrrolidone; polyethylene glycols; water; and mixtures thereof; - volatile silicones, octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), polydimethylsiloxane oils (PDMS), polyphenylmethylsiloxane oils (PPMS) or mixtures thereof; the solvent preferably being chosen from the group consisting of water, anisole and ethyl acetate, more preferably water and anisole.

8. Hydrosilylation process according to any one of claims 1 to 7, in which the reagents and solvents are used without a prior purification step.

9. Hydrosilylation process according to any one of claims 1 to 8, for the functionalization of organopolysiloxanes with SiH functions, characterized in that the unsaturated compound A comprising at least one monosubstituted alkene function is chosen from unsaturated compounds comprising one or more monosubstituted alkene functions and from 2 to 40 carbon atoms, and the compound B comprising at least one hydrogenosilyl function is an organopolysiloxane compound comprising at least one hydrogen atom bonded to a silicon atom.

10. Hydrosilylation process according to any one of claims 1 to 8, for the preparation of crosslinked silicone materials, characterized in that the unsaturated compound A comprising at least one monosubstituted alkene function is an organopolysiloxane compound comprising at least two monosubstituted alkene functions, and the compound B comprising at least one hydrogenosilyl function is an organopolysiloxane compound comprising at least three hydrogen atoms linked to a silicon atom.

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