Manganese complex-catalyzed hydrosilylation process

Abstract

The present invention relates to a hydrosilylation reaction between a monosubstituted alkene compound and a compound containing at least one hydrogen atom bonded to a silicon atom. More specifically, the present invention relates to a method for hydrosilylation of an unsaturated compound A containing at least one monosubstituted alkene group with a compound B containing at least one hydrosilyl group in the presence of air and / or water using a manganese complex C in the I oxidation state as a catalyst. This hydrosilylation reaction between an alkene compound and a compound containing at least one hydrogen atom bonded to a silicon atom particularly enables crosslinking of silicone compositions.

Description

[Technical Field]

[0001] The present invention relates to a hydrosilylation reaction between a monosubstituted alkene compound and a compound containing at least one hydrogen atom bonded to a silicon atom. More specifically, the present invention relates to a hydrosilylation process catalyzed by a manganese complex. In particular, the hydrosilylation reaction between an alkene compound and a compound containing at least one hydrogen atom bonded to a silicon atom enables crosslinking of silicone compositions. [Background technology]

[0002] The hydrosilylation (also called polyaddition) reaction of alkene compounds involves the reaction of a compound containing at least one double bond with a compound containing at least one hydrosilyl group (i.e., a hydrogen atom bonded to a silicon atom). This reaction can be described, for example, as follows: [ka]

[0003] The hydrosilylation reaction may be accompanied by, or in some cases replaced by, a dehydrosilylation reaction (also called dehydrosilylation), which can be written as follows: [ka]

[0004] The hydrosilylation reaction is used in particular to crosslink silicone compositions that contain organopolysiloxanes having alkenyl units and organopolysiloxanes that contain hydrosilyl functional groups.

[0005] The hydrosilylation reaction of alkene compounds is usually carried out by catalytic reaction using a metal catalyst or an organometallic catalyst. Currently, the catalyst suitable for this reaction is a platinum catalyst. Therefore, the majority of industrial hydrosilylation processes, especially the hydrosilylation process of alkenes, are catalyzed by Speier's hexachloroplatinic acid or Karstedt's Pt(0) complex of the general formula Pt2(divinyltetramethyldisiloxane)3 (abbreviated as Pt2(DVTMS)3).

[0006] In the early 2000s, the preparation of platinum carbene complexes enabled the availability of more stable catalysts (see, for example, patent application WO 01 / 42258).

[0007] However, the use of platinum metal catalysts and organometallic catalysts remains problematic. Platinum metal is an expensive metal, becoming increasingly scarce, and its price fluctuates widely, making its use on an industrial scale difficult. Therefore, it is desirable to minimize the amount of catalyst required for the reaction without compromising yield or reaction rate. Much research has been done to find alternatives to the Karstedt catalyst.

[0008] Over the past decade, the use of homogeneous manganese catalysts in organic synthesis has been gaining attention as an alternative. The scientific paper "Homogeneous Manganese-Catalyzed Hydrofunctionalizations of Alkenes and Alkynes: Catalytic and Mechanistic Tendencies" (ACS Omega 2022, 7, 37008-37038) by Antonio Torres-Calis and Juventino J. Garci provides a comprehensive review of manganese-based catalyst systems proposed for the hydrosilylation of alkenes. The scientific paper "Manganese-catalyzed divergent silylation of alkenes" (Nature Chemistry, vol. 13, Feb 2021, 182-190) by Dong et al. describes manganese-based catalysts for the dehydrosilylation and hydrosilylation of alkenes. Mn(CO) 10 Mn(CO) is used as a metal precursor and must be combined with a ligand, preferably a JackiePhos ligand, to promote the hydrosilylation reaction. 10 The manganese in the complex has an oxidation state of 0.

[0009] Yang X. and Wang C. ("Diverse Fates of β-silyl Radical under Manganese Catalysis: Hydrosilylation and Dehydrogenative Silylation of Alkenes," Chin. J. Chem. 2018, 36, 1047-1051) reported the chemoselective and regioselective hydrosilylation of alkenes catalyzed by MnBr(CO)5 complexes. The authors demonstrated the radical nature of the reaction mechanism. The hydrosilylation process was carried out under an inert atmosphere in the absence of air and water. All experiments were carried out in a dry Schlenk flask under an inert atmosphere. Solvents were purified by sodium distillation and stored under a nitrogen atmosphere.

[0010] More recently, a scientific paper (Anthony Vivien, Laurent Veyre, Raphael Mirgalet, Clement Camp, Chlole Thieuleux, "Mn2(CO) 10 and UV light: a promising combination for regioselective alkene hydrosilylation at low temperature,” Chem. Commun., 2022, 58, 4091-4094), and another manganese-based catalyst, [Mn(CO) 10 The use of dimanganese decacarbonyl ([Chemical Formula 1]) is described. Advantageously, it is commercially available, inexpensive, and air-stable. However, the hydrosilylation reaction itself is always carried out under an inert atmosphere, in a dry flask under argon. Reagents and solvents are purified and stored in a glove box under argon. Summary of the Invention [Problem to be solved by the invention]

[0011] Due to the radical mechanism of the reaction, there is a technical preconception that the catalysts described in the prior art must be used under anhydrous conditions, in the absence of air and water. Furthermore, other reagents and solvents must be purified and dried before use. From an industrial point of view, meeting these conditions is difficult and expensive.

[0012] Against this background, the present inventors sought a more efficient process for the hydrosilylation of alkene compounds. Advantageously, it would be desirable to overcome the limitations of the reaction, namely, its sensitivity to air and moisture. Furthermore, it would be desirable for the hydrosilylation reaction to proceed rapidly and selectively at moderate temperatures, and particularly for the dehydrosilylation and / or isomerization reactions of alkene compounds to be reduced or negligible. Finally, it would be desirable for the catalyst to contain abundant, inexpensive, and non-toxic chemical elements. [Means for solving the problem]

[0013] Contrary to expectations, the inventors have discovered that a catalyst based on manganese in the I oxidation state can be used advantageously in the presence of water and air. The inventors have discovered that the hydrosilylation reaction of monosubstituted alkenes can be catalyzed by manganese complexes in the I oxidation state in excellent yields and with excellent selectivity under industrially similar conditions, in air, and using unpurified reagents.

[0014] The present invention relates to a process for the hydrosilylation of an unsaturated compound A containing at least one monosubstituted alkene functional group with a compound B containing at least one hydrosilyl functional group, in the presence of air and / or water, catalyzed by a manganese complex in oxidation state C. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 shows Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0016] Unless otherwise specified, all viscosities of silicone oils discussed herein correspond to "Newtonian" kinematic viscosity quantities at 25°C, i.e., kinematic viscosities measured in a manner known per se using a Brookfield viscometer at shear rate gradients sufficiently low that the measured viscosity is independent of the rate gradient.

[0017] Although not depicted, possible tautomeric forms of the compounds described herein are included within the scope of the present invention.

[0018] In the present invention, the alkyl group may be linear or branched. The alkyl group preferably contains 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms. The alkyl group can be selected from, for example, 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.

[0019] In the present invention, the cycloalkyl group may be monocyclic or polycyclic, preferably monocyclic or bicyclic. The cycloalkyl group preferably contains 3 to 30 carbon atoms, more preferably 3 to 8 carbon atoms. The cycloalkyl group may be selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantane, and norborane.

[0020] In the present invention, the aryl group may be monocyclic or polycyclic, preferably monocyclic, and preferably contains 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms. The aryl group may be unsubstituted or substituted one or more times with an alkyl group. The aryl group may be selected from a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a mesityl group, a tolyl group, a xylyl group, a diisopropylphenyl group, and a triisopropylphenyl group.

[0021] In the present invention, the arylalkyl group preferably contains 6 to 30 carbon atoms, more preferably 7 to 20 carbon atoms. The arylalkyl group may, for example, be selected from the following group: benzyl, phenylethyl, phenylpropyl, naphthylmethyl, naphthylethyl and naphthylpropyl.

[0022] In the present invention, the halogen atom is selected from the group consisting of, for example, fluorine, bromine, chlorine and iodine, and is preferably fluorine. An example of a fluorine-substituted alkyl group is trifluoropropyl.

[0023] The present invention uses a manganese(I) complex, i.e., catalyst C, in the I oxidation state. Manganese is an abundant natural element and has the advantage that it is generally considered non-toxic within the range of intakes considered to be trace elements. In the present invention, the manganese(I) complex is a metal complex consisting of one or more manganese atoms in the I oxidation state and a ligand bound to the manganese.

[0024] A manganese(I) complex according to the invention may be a metal complex consisting of one or more manganese atoms in the I oxidation state, a carbonyl ligand, and an X-type ligand bound to the manganese. By definition, an X-type ligand contributes only one electron to the coordination sphere of the metal to which it is bound.

[0025] According to one embodiment, the manganese(I) complex may be chosen from complexes of formula Mn(CO)5Z, where Z represents a coordinating or non-coordinating anion. Z may be, for example, H - , F - , Cl - , Br - , I - , O.H. - , BF4 - , PF6 - , NO3 - , ClO4 - , R.C.O.O. - , CF3COO - , RSO3 - , BH4 - , BR4 - , AlR4 - , Al(OR)4 - , NH2 - , R.O. - , C.N. - , R2N - , SCN - , OCN - , OCP - , R.S. - , R - CONH - , (R-CO)N - , HCO3 - , HSO4 - , H2PO4 - , acetylacetonate, pentafluorobenzoate, bis(trimethylsilyl)amide, tetrakis[pentafluorophenyl]borate, and tetrakis[3,5-bis(trifluoromethyl)phenyl]borate; R can be selected from the group consisting of C 1~10 Alkyl groups, CF3, C2F5, C(CF3)3, C 3~10 Cycloalkyl groups, C containing at least one N, O or S heteroatom 3~10 Heterocyclic groups, C5~10 an aryl group or a C containing at least one N, O or S heteroatom 5~10 represents a heteroaryl group.

[0026] Highly preferred is the manganese(I) complex pentacarbonylmanganese(I) bromide, specifically represented by the chemical formula [MnBr(CO)5] (CAS number: 14516-54-2), which is advantageously commercially available, inexpensive and air-stable.

[0027] Catalysts C according to the invention are advantageously used without organic ligands, in particular - no nitrogen-based ligands (e.g. pyridine ligands), and / or - no phosphorus-based ligands (e.g. phosphine ligands) and / or - no acyl ligands, and / or -does not have diketone ligands (e.g., β-diketone ligands), and / or - free of substituted or unsubstituted cyclopentadienyl ligands, and / or - No organometallic ligands (e.g. triphenylarsine).

[0028] The molar concentration of catalyst C can be 0.01 mol % to 15 mol %, more preferably 0.05 mol % to 10 mol %, more preferably 0.1 mol % to 5 mol %, and even more preferably 0.2 mol % to 2 mol %, relative to the total number of moles of unsaturation possessed by unsaturated compound A.

[0029] According to a preferred variant, the process according to the invention does not use compounds based on platinum, palladium, ruthenium or rhodium, and the amount of compounds based on platinum, palladium, ruthenium or rhodium in the reaction medium is, for example, less than 0.1% by weight, preferably less than 0.01% by weight, and even more preferably less than 0.001% by weight, relative to the weight of catalyst C.

[0030] In the hydrosilylation process of the present invention, the unsaturated compound A used contains at least one monosubstituted alkene functional group. The monosubstituted alkene unsaturated group is not part of an aromatic ring. The unsaturated compound A is known to those skilled in the art and can be selected from those that do not contain reactive chemical functional groups that may interfere with or even inhibit the hydrosilylation reaction.

[0031] As used herein, "monosubstituted alkene" or "monosubstituted alkenyl" refers to a covalent double bond between two carbon atoms that are not part of an aromatic ring, and the two carbon atoms are bonded to three hydrogen atoms and a monovalent radical other than a hydrogen atom. The unsaturated compound A used in the hydrosilylation process of the present invention can be represented by the general formula (1): RCH=CH2(1) In the formula, R represents a monovalent radical.

[0032] According to one embodiment, the unsaturated compound A comprises one or more monosubstituted alkene functional groups and 2 to 40 carbon atoms. The unsaturated compound A is represented by the general formula (1): RCH=CH2(1) wherein R represents a monovalent radical selected from the group consisting of: an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms, optionally substituted with one or more halogen atoms such as chlorine or fluorine, and optionally substituted with one or more groups selected from —OH and —OSiR′3, where each R′ independently represents H or an alkyl group; aryl groups having 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, optionally substituted with one or more halogen atoms such as chlorine or fluorine, and optionally substituted with one or more groups selected from alkyl groups, haloalkyl groups, -OH, -OR', and -OSiR'3, where each R' independently represents H or an alkyl group; arylalkyl groups, preferably containing 6 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, the aryl and / or alkyl portions of which are optionally substituted with one or more halogen atoms such as chlorine or fluorine, and optionally substituted with one or more groups selected from alkyl groups, haloalkyl groups, —OH and —OR′ and —OSiR′3, where each R′ independently of the others represents H or an alkyl group; - an ether group of the formula -LOR" where L represents a bond or a divalent radical, preferably an alkylene group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and R" represents a group selected from alkyl groups having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms, optionally substituted with one or more halogen atoms such as chlorine or fluorine, and optionally substituted with one or more groups selected from -OH and -OSiR'3, where each R' independently represents H or an alkyl group; an aryl group having 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, optionally substituted with one or more halogen atoms such as chlorine or fluorine, and optionally substituted with one or more groups selected from -OH and -OSiR'3, where each R' represents, independently of one another, H or an alkyl group; an aryl group having 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, optionally substituted with chlorine; or fluorine, and optionally substituted with one or more groups selected from alkyl groups, haloalkyl groups, -OH, -OR', and -OSiR'3, where each R' independently represents H or an alkyl group; and arylalkyl groups, preferably containing 6 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, the aryl portion and / or the alkyl portion thereof, optionally substituted with one or more halogen atoms, such as chlorine or fluorine, and optionally substituted with one or more groups selected from alkyl groups, haloalkyl groups, -OH, -OR', and -OSiR'3, where each R' independently represents H or an alkyl group; an ester group of the formula -LC(O)-OR" or -LOC(O)-R" where L and R" have the same definitions as above.

[0033] The unsaturated compound A is preferably an organic compound containing a monosubstituted alkene group selected from the group consisting of: α-olefins, preferably 1-octene and 1-hexene, chlorinated α-olefins, preferably allyl chloride, fluorinated α-olefins, preferably 4,4,5,5,6,6,7,7,7-nonafluoro-1-heptene, allyl alcohol, allyl ethers, such as allyl benzyl ether, allyl phenyl ether, allyl C1-C8 alkyl ethers, allyl glycidyl ether, allyl ethers of piperidine, preferably allyl ethers of sterically hindered piperidine, allyl silyl ethers, preferably allyl trimethylsilyl ether, aliphatic alkenoic acid esters (e.g., C1-C4 alkyl acrylates), acrylic acid, allyl esters (e.g. allyl acetate), -styrene, allylbenzene, phenyl α-olefins, -1,2-epoxy-4-vinylcyclohexane.

[0034] The unsaturated compound A may be a disiloxane such as vinylpentamethyldisiloxane or divinyltetramethyldisiloxane.

[0035] The unsaturated compound A can be selected from compounds containing several monosubstituted alkene functional groups, preferably two or three monosubstituted alkene functional groups, particularly preferably the compound A is selected from the following compounds: [ka] [ka] [ka] [ka] [ka]

[0036] According to a particularly preferred embodiment, the unsaturated compound A may be an organopolysiloxane compound containing one or more monosubstituted alkene functional groups, preferably at least two monosubstituted alkene functional groups. The hydrosilylation reaction of alkenes is one of the important reactions in silicone chemistry. This allows crosslinking between organopolysiloxanes containing SiH functional groups and organopolysiloxanes containing alkenyl functional groups, forming a network that not only imparts mechanical properties to the material, but also allows functionalization of organopolysiloxanes containing SiH functional groups to modify their physical and chemical properties.

[0037] The organopolysiloxane compound may in particular be formed from: at least two siloxyl units of the formula: Y a R 1 b SiO (4-a-b) / 2 During the ceremony: Y is C2~C 12 is a mono-substituted alkenyl group, preferably a vinyl group, R 1 is a monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably selected from alkyl groups having 1 to 8 carbon atoms (e.g., methyl, ethyl, propyl), cycloalkyl groups having 3 to 8 carbon atoms, and aryl groups having 6 to 12 carbon atoms; a=1, 2, or 3, preferably a=1 or 2, more preferably a=1 and b=0, 1, or 2; the sum of a+b=1, 2, or 3; and Optionally, a unit having the formula: R 1 c SiO (4-c) / 2 In the formula, R 1 has the same meaning as above, and c=0, 1, 2 or 3.

[0038] In the above formula, multiple R 1 It is understood that when a group is present or when multiple Y groups are present, they may be the same or different from one another.1 R can represent a monovalent radical selected from the group consisting of alkyl groups having 1 to 8 carbon atoms (optionally substituted with 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. 1 can be advantageously selected from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl.

[0039] These organopolysiloxane compounds containing one or more monosubstituted alkene functional groups can have a linear, cyclic, or branched structure.

[0040] In the section below describing unsaturated organopolysiloxanes, the following nomenclature is used to represent the siloxyl units: - "M Vi The siloxyl units have the formula YR 1 2SiO 1 / 2 or Y2R 1 SiO 1 / 2 represents a siloxyl unit of - "M" siloxyl units have the formula R 1 3SiO 1 / 2 represents a siloxyl unit of - "D Vi The siloxyl units have the formula YR 1 SiO 2 / 2 represents a siloxyl unit of - "D" siloxyl units have the formula R 1 2SiO 2 / 2 represents a siloxyl unit of - "T" siloxyl units have the formula R 1 SiO 3 / 2 represents a siloxyl unit of - "Q" siloxyl units have the formula SiO 4 / 2 represents a siloxyl unit of Symbols Y and R 1 is as above.

[0041] Terminal "M" and "M ViExamples of siloxyl units include trimethylsiloxy, dimethylphenylsiloxy, dimethylvinylsiloxy or dimethylhexenylsiloxy groups.

[0042] "D" and "D Vi Examples of siloxyl units include dimethylsiloxy, methylphenylsiloxy, methylvinylsiloxy, methylbutenylsiloxy, methylhexenylsiloxy, methyldecenylsiloxy or methyldecadienylsiloxy groups.

[0043] Linear organopolysiloxane compounds containing one or more monosubstituted alkene functional groups are essentially "D" and "D Vi " siloxyl units and "M" and "M Vi Examples of linear organopolysiloxanes that may be organopolysiloxane compounds containing one or more monosubstituted alkene functional groups according to the present invention are as follows: -dimethylvinylsilyl terminated poly(dimethylsiloxane); -dimethylvinylsilyl terminated poly(dimethylsiloxane-co-methylphenylsiloxane); -dimethylvinylsilyl-terminated poly(dimethylsiloxane-co-methylvinylsiloxane); and -Trimethylsilyl terminated poly(dimethylsiloxane-co-methylvinylsiloxane).

[0044] In a most preferred embodiment, the organopolysiloxane compound containing one or more mono-substituted alkene functional groups is terminated with dimethylvinylsilyl groups, and more preferably, the organopolysiloxane compound containing one or more mono-substituted alkene functional groups is a poly(dimethylsiloxane) terminated with dimethylvinylsilyl groups.

[0045] The viscosity of silicone oils is generally 1 mPa s to 2,000,000 mPa s. Preferably, the organopolysiloxane compound containing one or more alkene functional groups is a silicone oil having a kinematic viscosity at 25°C of 20 mPa s to 100,000 mPa s, preferably 20 mPa s to 80,000 mPa s, and more preferably 100 mPa s to 50,000 mPa s.

[0046] The cyclic organopolysiloxane compounds containing one or more monosubstituted alkene functional groups are essentially the same as those described above under "D" and "D Vi " siloxyl units. An example of a cyclic organopolysiloxane that may be an organopolysiloxane compound containing one or more mono-substituted alkene functional groups according to the present invention is cyclic poly(methylvinylsiloxane).

[0047] Optionally, the organopolysiloxane compound containing one or more mono-substituted alkene functional groups may contain "T" siloxyl units and / or "Q" siloxyl units. In this case, the organopolysiloxane compound containing one or more mono-substituted alkene functional groups has a branched structure. Examples of branched organopolysiloxanes, also called resins, that may be organopolysiloxane compounds containing one or more mono-substituted alkene functional groups according to the present invention are as follows: -MD Vi Q (vinyl group contained in D unit), -MD Vi TQ (vinyl group contained in D unit), -MM Vi Q (wherein the vinyl group is part of the M unit), -MM Vi TQ (vinyl group is included as part of the M unit), -MM Vi DD Vi Q (vinyl groups are included in some of the M and D units), - and mixtures thereof.

[0048] Preferably, the organopolysiloxane compound containing one or more mono-substituted alkene functional groups has a weight content of mono-substituted alkenyl units of 0.001% to 30%, preferably 0.01% to 10%, preferably 0.02% to 5%.

[0049] According to the present invention, an unsaturated compound A is reacted with a compound B containing at least one hydrosilyl functional group.

[0050] According to one embodiment, the compound B containing at least one hydrosilyl group is a silane or polysilane compound containing at least one hydrogen atom bonded to a silicon atom. In the present invention, a "silane" compound is understood to mean a compound containing a silicon atom bonded to four hydrogen atoms or organic substituents. In the present invention, a "polysilane" compound is understood to mean a compound having at least one ≡Si-Si≡ unit. Among the silane compounds, the compound B containing at least one hydrosilyl group is a mono-, di-, or tri-alkylsilane, or a mono-, di-, or tri-arylsilane, such as triethylsilane, phenyldimethylsilane, benzyldimethylsilane, or diphenylsilane.

[0051] According to another embodiment, the compound B containing at least one hydrosilyl group is an organopolysiloxane compound in which at least one hydrogen atom is bonded to a silicon atom, also called organohydropolysiloxane, which is preferably an organopolysiloxane composed of: at least two siloxyl units of the formula: H d R 2 e SiO (4-d-e) / 2 During the ceremony: R 2 is a monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably selected from alkyl groups having 1 to 8 carbon atoms (e.g., methyl, ethyl, or propyl), cycloalkyl groups having 3 to 8 carbon atoms, and aryl groups having 6 to 12 carbon atoms; d=1, 2 or 3, preferably d=1 or 2, more preferably d=1, e=0, 1 or 2, d+e=1, 2 or 3; and -Optionally, other units of the formula: R 2 f SiO (4-f) / 2 In the formula, R 2 has the same meaning as above, and f=0, 1, 2 or 3.

[0052] In the above formula, multiple R 2 It is understood that when groups are present, they may be the same or different from one another. 2 R can represent a monovalent radical selected from the group consisting of alkyl groups having 1 to 8 carbon atoms (optionally substituted with 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. 2 can be advantageously selected from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl.

[0053] The organohydropolysiloxane may have a linear, branched, or cyclic structure, and the degree of polymerization is preferably 2 or more and usually less than 5,000.

[0054] In the section below describing organohydropolysiloxanes, the following nomenclature is used to represent the siloxyl units: - "M" siloxyl units have the formula R 2 3SiO 1 / 2 represents a siloxyl unit of - "M'" siloxyl units have the formula HR 2 2SiO 1 / 2 represents a siloxyl unit of - "D" siloxyl units have the formula R 2 2SiO 2 / 2 represents a siloxyl unit of - "D'" siloxyl units have the formula HR 2 SiO2 / 2 represents a siloxyl unit of - "T" siloxyl units have the formula R 2 SiO 3 / 2 represents a siloxyl unit of - "Q" siloxyl units have the formula SiO 4 / 2 represents a siloxyl unit of Symbol R 1 is as above.

[0055] In the case of linear polymers, these consist essentially of siloxyl units selected from "D" and "D'" siloxyl units and terminal "M" and "M'" siloxyl units. Examples of organohydropolysiloxanes which can be compound B containing at least one hydrosilyl group according to the invention are: -hydrodimethylsilyl-terminated poly(dimethylsiloxane); -trimethylsilyl-terminated poly(dimethylsiloxane-co-methylhydrosiloxane); -hydrodimethylsilyl group-terminated poly(dimethylsiloxane-co-methylhydrosiloxane); and - Trimethylsilyl terminated poly(methylhydrosiloxane).

[0056] When the organohydrogenpolysiloxane has a cyclic structure, it consists essentially of siloxyl units selected from "D" siloxyl units and "D'" siloxyl units. An example of a cyclic organohydropolysiloxane that may be compound B containing at least one hydrosilyl functional group according to the present invention is cyclic poly(methylhydrosiloxane).

[0057] When the organohydropolysiloxane has a branched structure, it is preferably selected from the group consisting of silicone resins of the following formula: -M'Q, in which the hydrogen atom bonded to the silicon atom is bonded to the M group, -MM'Q, in which the hydrogen atom bonded to the silicon atom is bonded to part of the M unit; -MD'Q, in which the hydrogen atom bonded to the silicon atom is bonded to a D group, -MDD'Q, in which the hydrogen atom bonded to the silicon atom is bonded to part of the D group, -MM'TQ, in which the hydrogen atom bonded to the silicon atom is bonded to part of the M unit; -MM'DD'Q, in which the hydrogen atom bonded to the silicon atom is bonded to part of the M and D units; - and mixtures thereof.

[0058] Preferably, the organohydropolysiloxane compound has a weight content of Si—H hydrosilyl functional groups of 0.2% to 91%, more preferably 3% to 80%, and even more preferably 15% to 70%.

[0059] The amounts of compound A and compound B can be controlled so that the molar ratio of the hydrosilyl functional group of compound B to the mono-substituted alkene functional group of compound A is preferably 1:10 to 10:1, more preferably 1:5 to 5:1, even more preferably 1:3 to 3:1, and even more preferably 1:2 to 2:1.

[0060] According to a specific embodiment of the present invention, the unsaturated compound A and compound B containing at least one hydrosilyl functional group can be one and the same compound, which first contains at least one monosubstituted alkene functional group and second contains at least one silicon atom and at least one hydrogen atom bonded to the silicon atom. This compound is described as "bifunctional" and can react with itself via a hydrosilylation reaction. Therefore, the present invention also relates to a process for the hydrosilylation of a bifunctional compound containing first contains at least one monosubstituted alkene functional group and second contains at least one silicon atom and at least one hydrogen atom bonded to the silicon atom, which process is catalyzed by the above-mentioned catalyst C.

[0061] Examples of organopolysiloxanes that can be difunctional compounds are as follows: -dimethylvinylsilyl terminated poly(dimethylsiloxane-co-hydromethylsiloxane-co-vinylmethylsiloxane); -dimethylhydrosilyl-terminated poly(dimethylsiloxane-co-hydromethylsiloxane-co-vinylmethylsiloxane); and - Trimethylsilyl terminated poly(dimethylsiloxane-co-hydromethylsiloxane-co-propylglycidyl ether methylsiloxane).

[0062] Those skilled in the art will understand that when the use of an unsaturated compound A and a compound B containing at least one hydrosilyl function is in question, this also means the use of a bifunctional compound.

[0063] The process of the present invention is particularly characterized in that the hydrosilylation reaction is carried out in the presence of air and / or water. In particular, it has been surprisingly discovered that the reaction is not affected by air and moisture.

[0064] The hydrosilylation process according to the invention is preferably carried out in air and not under an inert atmosphere, in particular not under nitrogen, argon or oxygen-depleted air.

[0065] The hydrosilylation reaction can be carried out at a temperature of 15°C to 300°C, preferably 20°C to 240°C, more preferably 50°C to 200°C, even more preferably 50°C to 140°C, and even more preferably 50°C to 100°C.

[0066] The hydrosilylation reaction can be carried out in a solvent or without a solvent. Suitable solvents are those that are 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 liquid paraffin; aromatic hydrocarbons such as toluene and xylene; mixtures of mineral or synthetic hydrocarbons 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 glycol; water; and mixtures thereof. Preferably, the solvent is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and chlorinated hydrocarbons, and more preferably, the group consisting of hexane, cyclohexane, decalin, and toluene.

[0067] Alternatively, the solvent can be selected from volatile silicones, octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), polydimethylsiloxane (PDMS) oil, polyphenylmethylsiloxane (PPMS) oil, or mixtures thereof. Alternatively, one of the reagents, for example the unsaturated compound A, can be used as the solvent. It is desirable to avoid the use of organic solvents, which are harmful to the environment and the health of workers in the manufacturing plant.

[0068] In another variant, the solvent can be selected from the most environmentally friendly solvents. For example, see the scientific papers by Alder et al. (Green Chem., 2016, 18, 3879) or Prat et al. (Green Chem., 2016, 18, 288). Preferably, the solvent is selected from the group consisting of water, anisole and ethyl acetate, more preferably water and anisole.

[0069] When a solvent is present, those skilled in the art can adjust the amount of solvent to ensure good miscibility of the reagents. For example, the amount of solvent can be 5% to 70%, preferably 10% to 50%, of the total volume of the reaction medium.

[0070] Advantageously, the reagents and solvents used in the process of the present invention can be used without prior purification steps, and it has been surprisingly observed that the performance of the hydrosilylation reaction obtained using unpurified reagents is comparable to that obtained using purified reagents.

[0071] The discovery of this new hydrosilylation process by the present invention has many potential applications.

[0072] When the compounds A and B used are selected from organopolysiloxanes as defined above, a hydrosilylation reaction allows the formation of a three-dimensional network, leading to the curing or crosslinking of the composition. Crosslinking involves a gradual physical change of the medium constituting the composition. Therefore, the method of the present invention can be used to produce elastomers, gels, foams, etc. In this case, a crosslinked silicone material is obtained. "Crosslinked silicone material" is understood to mean a silicone-based product obtained by crosslinking and / or curing a composition comprising an organopolysiloxane having at least two unsaturated bonds and an organopolysiloxane having at least three hydrosilyl units. The crosslinked silicone material may be, for example, an elastomer, gel, or foam.

[0073] In this preferred embodiment of the method of the present invention, when compounds A and B are selected from the organopolysiloxanes defined above, conventional functional additives can be used in silicone compositions. Common families of functional additives include: -fillers, adhesion promoters, inhibitors or retarders of the hydrosilylation reaction, -adhesion modifiers, silicone resin, - viscosity improvers, pigments (organic or mineral), and - Heat-, oil- or fire-resistant additives (e.g. metal oxides).

[0074] The optionally added filler is preferably a mineral filler. The filler may be a very fine product with an average particle size of less than 0.1 μm. The filler may in particular be a siliceous filler. The siliceous material may act as a reinforcing or semi-reinforcing filler. The reinforcing filler is selected from colloidal silica, fumed silica, and precipitated silica powders, or mixtures thereof. The average particle size of these powders is usually less than 0.1 μm (micrometer) and the BET specific surface area is 30 m 2 / g or more, preferably 30 to 350m 2 / g. Semi-reinforcing siliceous fillers such as diatomaceous earth and ground quartz can also be used. These silicas can be incorporated unmodified or after treatment with organosilicon compounds commonly used for this purpose. These compounds include methylpolysiloxanes such as hexamethyldisiloxane and octamethylcyclotetrasiloxane; methylpolysilazanes such as hexamethyldisilazane, hexamethylcyclotrisilazane, and tetramethyldivinyldisilazane; chlorosilanes such as dimethyldichlorosilane, trimethylchlorosilane, methylvinyldichlorosilane, and dimethylvinylchlorosilane; alkoxysilanes such as dimethyldimethoxysilane, dimethylvinylethoxysilane, and trimethylmethoxysilane; and mixtures thereof. Non-siliceous inorganic materials can be used as semi-reinforcing or extending inorganic fillers. Examples of these non-siliceous fillers, which can be used alone or in admixture, include calcium carbonate (optionally surface treated with an organic acid or organic acid ester), calcined clay, rutile titanium dioxide, iron oxide, zinc oxide, chromium oxide, zirconium oxide, magnesium oxide, various forms of alumina (hydrated or non-hydrated), boron nitride, lithopone, barium metaborate, barium sulfate, and glass microbeads. These fillers are coarse, with an average particle size generally greater than 0.1 μm and a specific surface area generally greater than 30 m. 2 / g. These fillers may be surface-modified by treatment with various organosilicon compounds commonly used for this purpose. Preferably, the filler is silica, more preferably fumed silica. The BET specific surface area of ​​silica is 75 m 2 / g~410m 2 Advantageously, the silicone composition may contain 5% to 20% by weight of filler relative to the total weight of the silicone composition. Preferably, the silicone composition may contain 8% to 15% by weight of filler.

[0075] In a particularly preferred embodiment, the hydrosilylation process according to the present invention is used to crosslink an organopolysiloxane containing SiH functional groups with an organopolysiloxane containing alkenyl functional groups, forming a network and imparting mechanical properties to the material. According to this embodiment, the unsaturated compound A containing at least one monosubstituted alkene functional group is an organopolysiloxane compound containing at least two monosubstituted alkene functional groups, and the compound B containing at least one hydrosilyl functional group is an organopolysiloxane compound containing at least three hydrogen atoms bonded to silicon atoms. A method for producing a crosslinked silicone material can be described, characterized in that the crosslinking reaction between the SiH group-containing organopolysiloxane and the alkenyl group-containing organopolysiloxane is achieved by the above-described hydrosilylation process. The resulting crosslinked silicone material can be used in a variety of applications, particularly the following: - "Coating" applications, where the substrate is covered with a silicone coating; -Applications in the electronics sector (e.g., the production of conformal coatings for printed circuits, potting of electronic components such as microcircuits and IGBTs); -Additive manufacturing processes (also known as 3D printing processes).

[0076] In another embodiment, the hydrosilylation process according to the present invention can be used to functionalize organopolysiloxanes containing SiH functional groups. The purpose of functionalization is to modify the physical and / or chemical properties of the organopolysiloxanes and produce new compounds with improved properties. According to this embodiment, the unsaturated compound A containing at least one monosubstituted alkene functional group is selected from unsaturated compounds containing one or more monosubstituted alkene functional groups and containing 2 to 40 carbon atoms, and the compound B containing at least one hydrosilyl functional group is an organopolysiloxane compound containing at least one hydrogen atom bonded to a silicon atom. A method for functionalizing organopolysiloxanes containing SiH functional groups can be described, characterized in that the addition reaction between the organopolysiloxane containing SiH functional groups and the unsaturated compound A containing one or more monosubstituted alkene functional groups and 2 to 40 carbon atoms is obtained by the hydrosilylation process described above.

[0077] Other details or advantages of the invention will become more apparent upon consideration of the examples given below, which are merely illustrative. [Example]

[0078] Comparative Example 1: The catalysts described in the prior art must be used under anhydrous conditions, in the absence of air and water. 10 The sensitivity of to air is demonstrated in the following Comparative Example 1 shown in Figure 1:

[0079] Styrene and 1,1,1,3,5,5,5-heptamethyltrisiloxane were introduced into a vial at room temperature under an argon atmosphere. 10 The toluene solution of Mn2(CO) was poured into a vial and toluene was added. 10 The final concentration (relative to styrene) was 2 mol %.

[0080] First, the reaction mixture was irradiated with UV light at room temperature for 30 minutes. The reaction medium was clear and pale yellow. After 30 minutes, the reaction medium was exposed to air. The reaction medium rapidly turned dark brown (see Figure 1), indicating that the catalytic reaction had stopped.

[0081] Examples 1 and 2: Hydrosilylation of 1-octene (1) with 1,1,1,3,5,5,5-heptamethyltrisiloxane (2) [ka]

[0082] Example 1: 1-octene (1) (74 μL, 0.47 mmol) and 1,1,1,3,5,5,5-heptamethyltrisiloxane (2) (256 μL, 0.94 mmol) were placed in a vial. A toluene solution of MnBr(CO)5 was injected into the vial, and toluene was added. The final concentration of [Mn] relative to 1-octene was 2 mol%. The total amount of toluene was 195 μL. The reaction was carried out in air, and the reagents and toluene were not purified.

[0083] After 4 hours at 70°C, the reaction yield was 99%. No isomerization products of 1-octene were detected. No dehydrosilylation products were observed. Therefore, the reaction is selective for hydrosilylation.

[0084] Example 2: 1-octene (1) (0.94 mmol) and 1,1,1,3,5,5,5-heptamethyltrisiloxane (2) (0.94 mmol) were used in a 1:1 molar ratio, and the same procedure as in Example 1 (70°C, 4 hours, in air, no purification) was followed. After 4 hours of reaction at 70°C, the yield was 96%. The isomerization rate of 1-octene was less than 1%.

[0085] Examples 3 to 16 and Comparative Examples 2 to 5: Hydrosilylation of Various Alkenes (1') [ka]

[0086] Following the same procedure as in Example 1 (70°C, 4 hours, in air, in toluene, without purification), the structure of alkene compound (1') was altered as shown in Table 1 below. The amount of reagent used was 1 equivalent of alkene (1') per 1 or 2 equivalents of heptamethyltrisiloxane (2). The yield of hydrosilylated product (3') (measured by gas chromatography and calculated relative to the alkene) is shown in Table 1.

[0087] [Table 1]

[0088] In Examples 3 to 16, hydrosilylated products were obtained with excellent selectivity. No C=C isomerization or C-O bond cleavage products were observed. However, no hydrosilylated products were obtained from gem-disubstituted alkenes (Comparative Examples 2, 3, and 5) or internal alkenes (Comparative Example 4).

[0089] Examples 17-33: Hydrosilylation in various solvents The same procedure as described in Example 1 (70°C, 4 hours, in air, without purification) was carried out, but with different solvents and alkenes, as shown in Tables 2 and 3. The yields of hydrosilylated product (3) (determined by gas chromatography, calculated relative to the alkene) are shown in Tables 2 and 3. [ka] Alkene (1) = 1-octene. Molar ratio of (1):(2) = 1:2 or 1:1.

[0090] [Table 2]

[0091] [ka] Various alkenes (1'). Molar ratio (1'):(2) = 1:1

[0092] [Table 3]

[0093] Examples 34-43: Hydrosilylation of various silanes Styrene (0.47 mmol, 1 equivalent) and the silane compound (0.94 mmol, 2 equivalents) were placed in a vial. A solution of MnBr(CO)5 in anisole was injected into the vial, and anisole was added. The final concentration of [Mn] relative to styrene was 2 mol%. The reaction was carried out in air at 70 °C, and the reagents and anisole were not purified. After 4 h, the yields of the hydrosilylated products (measured by gas chromatography, converted to the alkene) are shown in Table 4.

[0094] [Table 4]

[0095] The same procedure (70°C, 4 hours, in air, no purification) described above for Examples 34-37 was carried out using various alkenes and various silanes in a 1:1 molar ratio. After 4 hours, the yields of hydrosilylated products (determined by gas chromatography and calculated relative to the alkene) are shown in Table 5.

[0096] [Table 5]

[0097] Examples 34-43 show that hydrosilylation catalyzed by MnBr(CO)5 works not only with siloxane compounds (Examples 1-33) but also with silane compounds.

[0098] Examples 44-46: Effect of Reagent Purification The same procedure as in Example 1 (70°C, 4 hours, in air) was followed, except for the solvent (anisole was used instead of toluene). Various alkene compounds (1') were tested with or without purification, as shown in Table 6. The amounts of reagents used were 2 equivalents of heptamethyltrisiloxane (2) and 1 equivalent of alkene (1'). The final concentration of [Mn] relative to 1-octene was 2 mol%. The yields of hydrosilylated products (3') (calculated relative to the alkene by gas chromatography) are shown in Table 6.

[0099] [Table 6]

[0100] In Examples 44 and 46, no significant difference was observed between the use of purified and unpurified reagents. In Example 45, the yield decreased slightly, but this was due to the presence of butylcatechol in commercial styrene. Butylcatechol is a stabilizer that protects commercial styrene from radical reactions, which reduces catalytic activity in the hydrosilylation reaction.

[0101] Examples 47-49: Polysiloxane crosslinking reaction The hydrosilylation reaction proceeds approximately as follows: 50 This was carried out using a polymethylhydrosiloxane oil with an M structure (Si-H unit content of approximately 45.5 wt%).

[0102] Example 47: Polymethylhydrosiloxane oil (1 equivalent of SiH groups) and divinyltetramethyldisiloxane (1 equivalent of C=C groups) were mixed in a vial with 0.3 mol% MnBr(CO)5 relative to the number of moles of SiH. The reaction was carried out in air at 70°C without prior purification. After 8 hours, gelation, corresponding to crosslinking of the composition, was observed.

[0103] Example 48: Polymethylhydrosiloxane oil (1 equivalent of SiH groups) and diethyl diallylmalonate (1 equivalent of C=C groups) were mixed in a vial with 0.3 mol% MnBr(CO)5 relative to the number of moles of SiH. The reaction was carried out in air at 70 °C without prior purification. After 2 hours, gelation, corresponding to crosslinking of the composition, was observed.

[0104] Example 49: Unsaturated Compounds Vi D 64 M Vi The compound was an α,ω-divinylpolydimethylsiloxane oil with the following structure (vinyl unit content: approximately 1% by weight). The MnBr(CO)5 catalyst was diluted with toluene and mixed with a portion of the α,ω-divinylpolydimethylsiloxane oil. While stirring, the polymethylhydrosiloxane oil and the remaining α,ω-divinylpolydimethylsiloxane oil were added so that the SiH / SiVi molar ratio was 1.7 and the MnBr(CO)5 content was 2 mol% relative to the number of moles of SiH. The reaction was carried out in air at 100°C. After 23 minutes, a gel had formed throughout the flask.

[0105] Examples 50-56: Reactions with various functionalized alkenes The hydrosilylation reaction proceeds approximately as follows: 50 This was carried out using a polymethylhydrosiloxane oil with an M structure (Si-H unit content of approximately 45.5 wt%).

[0106] The same procedure as in Example 47 (70°C, in air, without purification) was carried out, varying the alkene compound as shown in Table 7 below. The gelling times of the reaction media are shown in Table 7.

[0107] [Table 7]

[0108] Examples 50-56 demonstrate that the MnBr(CO) catalyst catalyzes not only the hydrosilylation reaction between hydrosilyl groups and C=C unsaturated groups, but also the hydrosilylation reactions with acetate groups (Examples 50 and 51), acrylate groups (Examples 52 and 53), and ketone groups (Example 54). In Examples 55 and 56, crosslinking is achieved by ring-opening of the epoxide.

Claims

1. A process for the hydrosilylation of an unsaturated compound A containing at least one monosubstituted alkene functional group with a compound B containing at least one hydrosilyl functional group in the presence of air and / or water, catalyzed by a manganese complex in oxidation state C.

2. 2. The hydrosilylation process of claim 1, wherein the I oxidation state manganese complex has the formula Mn(CO) 5 Z complexes, wherein Z is H - , F - , Cl - ,Br - , I - , O.H. - , B.F. 4 - , P.F. 6 - , NO 3 - , ClO 4 - , RCOO - , C.F. 3 COO - , RSO 3 - , B.H. 4 - , B.R. 4 - , AlR 4 - , Al(OR) 4 - , N.H. 2 - , R.O. - , C.N. - , R 2 N - , SCN - , O.C.N. - , O.C.P. - , R.S. - , R - CONH - , (R-CO) 2 N - , HCO 3 - , HSO 4 - , H 2 P.O. 4 - , acetylacetonate, pentafluorobenzoate, bis(trimethylsilyl)amide, tetrakis[pentafluorophenyl]borate, and tetrakis[3,5-bis(trifluoromethyl)phenyl]borate; R represents a coordinating or non-coordinating anion selected from the group consisting of C 1～10 Alkyl group, CF 3 , C 2 F 5 , C(CF 3 ) 3 , C 3～10 Cycloalkyl groups, C containing at least one N, O or S heteroatom 3～10 Heterocyclic group, C 5～10 an aryl group or a C group containing at least one N, O or S heteroatom 5～10 represents a heteroaryl group.

3. Manganese complexes in the I oxidation state have the formula [MnBr(CO) 5 3. The hydrosilylation process according to claim 1 or claim 2, wherein the compound is pentacarbonylmanganese(I) bromide of the formula:

4. The hydrosilylation process according to any one of claims 1 to 3, wherein the unsaturated compound A comprises one or more monosubstituted alkene functional groups and 2 to 40 carbon atoms, and preferably the unsaturated compound A is represented by the general formula (1): RCH=CH 2 (1) During the ceremony, wherein R represents a monovalent radical selected from the group consisting of: - an alkyl group having from 1 to 30 carbon atoms, more preferably from 1 to 12 carbon atoms, even more preferably from 1 to 6 carbon atoms, optionally substituted with one or more halogen atoms such as chlorine or fluorine, and optionally -OH and -OSiR' 3 wherein each R' independently represents H or an alkyl group; - aryl groups having 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, optionally substituted with one or more halogen atoms such as chlorine or fluorine, and optionally alkyl groups, haloalkyl groups, -OH, -OR', and -OSiR'; 3 wherein each R' independently represents H or an alkyl group; arylalkyl groups, preferably containing 6 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, the aryl portion of which and / or the alkyl portion of which are optionally substituted with one or more halogen atoms such as chlorine or fluorine, and optionally alkyl groups, haloalkyl groups, -OH and -OR' and -OSiR' 3 wherein each R' independently represents H or an alkyl group; an ether group of the formula -L-O-R", where L represents a bond or a divalent radical, preferably an alkylene group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and R" represents a group selected from alkyl groups having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, optionally substituted with one or more halogen atoms such as chlorine or fluorine, and optionally -OH and -OSiR' 3 wherein each R' independently represents H or an alkyl group; an aryl group having 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, optionally substituted with one or more halogen atoms such as chlorine or fluorine, and optionally an alkyl group, a haloalkyl group, -OH, -OR', and -OSiR' 3 wherein each R' independently represents H or an alkyl group; and arylalkyl groups preferably containing 6 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, the aryl portion and / or the alkyl portion of which are optionally substituted with one or more halogen atoms such as chlorine or fluorine, and optionally alkyl groups, haloalkyl groups, -OH, -OR' and -OSiR'. 3 wherein each R' independently represents H or an alkyl group; an ester group of the formula -LC(O)-OR" or -LOC(O)-R" where L and R" have the same definitions as above.

5. 4. The hydrosilylation process according to claim 1, wherein the unsaturated compound A is an organopolysiloxane compound containing one or more mono-substituted alkene functional groups, preferably at least two mono-substituted alkene functional groups.

6. 6. The hydrosilylation process of claim 1, wherein the compound B containing at least one hydrosilyl functional group is an organopolysiloxane compound containing at least one hydrogen atom bonded to a silicon atom.

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

8. The hydrosilylation process of any one of claims 1 to 7, wherein the reagents and solvents are used without a prior purification step.

9. 9. A hydrosilylation process for functionalizing organopolysiloxanes bearing SiH functional groups according to any one of claims 1 to 8, wherein the unsaturated compound A containing at least one monosubstituted alkene functional group is selected from unsaturated compounds containing one or more monosubstituted alkene functional groups and containing from 2 to 40 carbon atoms, and the compound B containing at least one hydrosilyl functional group is an organopolysiloxane compound containing at least one hydrogen atom bonded to a silicon atom.

10. 9. A hydrosilylation process for producing a crosslinked silicone material according to any one of claims 1 to 8, wherein the unsaturated compound A containing at least one mono-substituted alkene functional group is an organopolysiloxane compound containing at least two mono-substituted alkene functional groups, and the compound B containing at least one hydrosilyl functional group is an organopolysiloxane compound containing at least three hydrogen atoms bonded to silicon atoms.

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