Hydrosilylation method catalyzed by cobalt complex

Abstract

The present invention relates to a process for hydrosilylation of an unsaturated compound with a compound containing at least one hydrosilyl functional group, which is catalyzed by an organocobalt compound in the presence of a compound (E) having the formula (3): R'OH, wherein R' represents a hydrogen atom or R' is selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group and a silyl group.

Description

Technical Field

[0001] Technical Field The present invention relates to hydrosilylation reactions of alkene or alkyne compounds with compounds containing at least one hydrogen atom bonded to a silicon atom. In particular, the present invention relates to the use of a novel type of catalyst for these reactions. These catalysts can be used, in particular, to cure silicone compositions by crosslinking.

Background Art

[0002] Prior Art During a hydrosilylation reaction (also called an addition polymerization reaction), an unsaturated compound, i.e., a compound containing at least one double bond or triple bond unsaturation, reacts with a compound containing at least one hydrosilyl functional group, i.e., a compound containing a hydrogen atom bonded to a silicon atom. This reaction can be illustrated, for example, in the case of alkene unsaturation by the following formula:

Chem.

Chem.

[0003] The hydrosilylation reaction may involve a dehydrogenative silylation reaction and may be replaced by it. This reaction can be illustrated by the following formula:

Chem.

[0004] The hydrosilylation reaction is used, in particular, to crosslink silicone compositions containing an organopolysiloxane having alkenyl or alkynyl units and an organopolysiloxane having hydrosilyl functional groups.

[0005] The hydrosilylation reaction of unsaturated compounds is typically carried out by catalysis using a metal catalyst or an organometallic catalyst. Currently, the catalyst suitable for this reaction is a platinum catalyst. Therefore, in particular, most industrial hydrosilylation processes for the hydrosilylation of alkenes are catalyzed by Speier's hexachloroplatinic acid or the Karstedt Pt(0) complex of the general formula Pt2(di vinyltetramethyldisiloxane)3 (abbreviated as Pt2(DVTMS)3).

[0006] In the 2000s, the production of platinum - carbene complexes made it possible to obtain more stable catalysts (see, for example, WO 01 / 42258).

[0007] However, there are still problems with the use of metal catalysts or organometallic catalysts containing platinum. Platinum is an expensive metal, its scarcity is increasing, and its cost is soaring. Therefore, its use on an industrial scale is difficult. Thus, it is desirable to minimize the amount of catalyst required for the reaction without reducing the yield and reaction rate. Numerous studies have been carried out to find alternatives to the Karstedt catalyst.

[0008] Against this background, research has been conducted for many years to find a new catalyst for carrying out the hydrosilylation of alkenes.

[0009] WO 2018 / 115601 describes the use of novel cobalt - based catalysts as hydrosilylation and / or dehydrogenosilylation catalysts. These novel catalysts have the general formula [Co(N(SiR3)2) x y ​represented by, wherein the symbol R may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, x is equal to 1, 2 or 3, and y is equal to 1 or 2. The present inventors have demonstrated that these novel catalysts can effectively catalyze hydrosilylation reactions and / or dehydrogenative silylation reactions, preferably without a solvent (since these catalysts have good solubility in silicone oil). However, these compounds were produced and handled in the absence of air and water. The hydrosilylation and / or dehydrogenative silylation processes were carried out under an inert atmosphere in a glove box. All examples were carried out under an inert atmosphere, inside a glove box and / or inside a sealed Schlenk flask.

[0010] Similarly, the cobalt catalyst is described in the paper "Mode of Activation of Cobalt(II)Amides for Catalytic Hydrosilylation of Alkenes with Tertiary Silanes" by Yang Liu and Liang Deng (J. Am. Chem. Soc. 2017, 139, 1798 - 180). The reaction was carried out under strict anhydrous conditions, under an inert atmosphere of dry nitrogen, especially in a glove box. The solvent was dried and degassed before use (see the Supporting Information of the same paper).

[0011] Therefore, there is a technical preconception that the catalysts described in the prior art must be produced, stored, and used under anhydrous conditions without air and water. Furthermore, other reagents and any solvents must be dried before use. From an industrial perspective, it is difficult to meet such conditions and it is also costly.

[0012] Furthermore, other documents describing hydrosilylation catalysts can be cited. WO 2016 / 099727 discloses a compound of the formula R 1 2P-X-N=C(R 2)-Y's specific ligand is used, and a hydrosilylation catalyst based on iron, cobalt, manganese, nickel, or ruthenium is described. International Publication No. 2005 / 028544 describes a heterogeneous catalyst composition containing at least one metal selected from cobalt, rhodium, ruthenium, platinum, and nickel and deposited on an inert carrier, wherein hydrosilylation is carried out in the presence of at least one inorganic non-nucleophilic base and optionally water.

Prior Art Documents

Patent Documents

[0013]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Non-Patent Documents

[0014]

Non-Patent Document 1

Summary of the Invention

Means for Solving the Problems

[0015] Summary of the Invention Contrary to all expectations, the inventor has found that the above cobalt catalyst can be advantageously used in the presence of water, alcohol, or silanol.

[0016] Accordingly, the present invention is a method for hydrosilylating an unsaturated compound (A) containing at least one functional group selected from an alkene functional group and an alkyne functional group with a compound (B) containing at least one hydrosilyl functional group, the method comprising the unsaturated compound (A), the compound (B), and a cobalt compound (C) of the following formula (1): [Co(N(SiR3)2) x y (1) (wherein · The symbol R may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, · x = 1, 2 or 3, · y = 1 or 2.) and a compound (D) of the following formula (2):

Chemical formula

[0017] Furthermore, the present invention relates to at least one unsaturated compound (A) containing at least one functional group selected from an alkene functional group and an alkyne functional group, a compound (B) containing at least one hydrosilyl functional group, and a cobalt compound (C) of the following formula (1): [Co(N(SiR3)2) x y (1) (wherein · the symbol R may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, · x = 1, 2 or 3, · y = 1 or 2.) and a compound (D) of the following formula (2):

Chemical formula

Embodiments for Carrying Out the Invention

[0018] Detailed Description of the Invention The symbol → in the text represents a coordinate covalent bond due to the presence of a lone pair of electrons in the ligand.

[0019] In this specification, in accordance with the standard notations in the technical field, the symbol "N" represents a nitrogen atom, the symbol "Co" represents a cobalt atom, the symbol "H" represents a hydrogen atom, and the symbol "P" represents a phosphorus atom.

[0020] Unless otherwise indicated, all viscosities of silicone oils related to this description are the "Newtonian" kinematic viscosity at 25 °C, that is, the kinematic viscosity measured at a shear rate gradient low enough that the measured viscosity does not depend on the velocity gradient, using a Brookfield viscometer by a method known per se.

[0021] Although not depicted, the possible tautomeric forms of the compounds described in this specification are included within the scope of the present invention.

[0022] 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, for example, 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.

[0023] In the present invention, the cycloalkyl group can 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 can be selected, for example, from the following groups: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, and norbornyl.

[0024] In the present invention, the aryl group can 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 with one or more alkyl groups. The aryl group can 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.

[0025] In the present invention, the arylalkyl group preferably contains 6 to 30 carbon atoms, more preferably 7 to 20 carbon atoms. The arylalkyl group can be selected from, for example, the following groups: benzyl, phenylethyl, phenylpropyl, naphthylmethyl, naphthylethyl, and naphthylpropyl.

[0026] In the present invention, the halogen atom can be selected from the group consisting of, for example, fluorine, bromine, chlorine, and iodine, with fluorine being preferred. The fluorine-substituted alkyl group can be, for example, trifluoropropyl.

[0027] The present invention is a novel method for hydrosilylating an unsaturated compound (A) and a compound (B) containing at least one hydrosilyl functional group, which is catalyzed by a cobalt compound (C) in the presence of a compound (D) and a compound (E) as described below.

[0028] The hydrosilylation reaction may involve a dehydrogenative silylation reaction. The cobalt compound (C) in the presence of the compound (D) and the compound (E) described below can also be advantageously used as a catalyst for the dehydrogenative silylation reaction between an unsaturated compound (A) containing at least one functional group selected from an alkene functional group and an alkyne functional group and a compound (B) containing at least one hydrosilyl functional group. In this specification, unless otherwise specified, comments and explanations regarding the hydrosilylation reaction also apply to the dehydrogenative silylation reaction.

[0029] The cobalt compound (C) is represented by the following formula: [Co(N(SiR3)2) x y (1) In the formula, · The symbol R may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, · x = 1, 2 or 3, · y = 1 or 2.

[0030] Preferably, the symbol R may be the same or different and is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an arylalkyl group having 7 to 24 carbon atoms. More preferably, the symbol R may be the same or different and is selected from the group consisting of a methyl group, an ethyl group, a propyl group, a xylyl group, a tolyl group and a phenyl group. Even more preferably, the R group is methyl.

[0031] In this formula (1), cobalt may be in an oxidation state of +I, +II or +III.

[0032] According to a preferred embodiment, x = 2. The cobalt compound (C) has the formula [Co(N(SiR3)2)2] y wherein R and y are as defined above. At this time, cobalt is in the +II oxidation state.

[0033] According to a highly preferred embodiment, the cobalt compound (C) is represented by the following formula: [Co(N(Si(CH3)3)2)2] y In the formula, y is equal to 1 or 2.

[0034] The cobalt compound (C) can be obtained commercially or can be prepared according to any method known to those skilled in the art or described in the literature. According to one embodiment, the cobalt compound (C) [Co(N(Si(CH3)3)2)2] y ​It can be produced by reacting cobalt halide, for example cobalt chloride CoCl2, with lithium bis(trimethylsilyl)amide LiN(SiMe3)2. This synthesis may be carried out before the hydrosilylation reaction, or the cobalt compound (C) may be synthesized in situ in the presence of the unsaturated compound (A).

[0035] The molar concentration of the cobalt element provided by the cobalt compound (C) may be 0.01 mol% to 15 mol%, more preferably 0.05 mol% to 10 mol%, still more preferably 0.1 mol% to 8 mol% based on the total number of moles of unsaturation held by the unsaturated compound (A). According to another variant, the amount of cobalt used in the process according to the invention is, on a weight basis, 10 ppm to 3000 ppm, more preferably 20 ppm to 2000 ppm, still more preferably 20 ppm to 1000 ppm, without considering the optional presence of the solvent, based on the total weight of the compounds (A), (B), (C), (D) and (E). According to a preferred variant, in the process according to the invention, compounds based on platinum, palladium, ruthenium or rhodium are not used. 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, more preferably less than 0.001% by weight based on the weight of the cobalt compound (C).

[0036] Compound (D) according to the invention is represented by the following formula (2).

Chemical formula

[0037] Preferably, in the above formula (2), ·A 1 , A 2 , A 3 and A 4 are hydrogen atoms, ·A 5 and A 6 are hydrogen atoms, ·A 7 and A 8 are an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, and a formula OA 10 (where A 10 is an alkyl group having 1 to 8 carbon atoms.) is selected from the alkoxy groups, preferably, A 7 and A 8 are selected from a t-butyl group, an isopropyl group, a methyl group, an ethyl group, a phenyl group and a cyclohexyl group.

[0038] More preferably, the compound (D) is selected from the compounds of the following formulas (4) to (9).

Chemical formula

[0039] Although it is not desired to be limited by any one theory, compound (C) and compound (D) can react partially or completely to form a complex. Compound (D) can act as a ligand that can coordinate cobalt via the lone pair of electrons possessed by a nitrogen atom, a phosphorus atom, or both. In this way, a cobalt complex (C') represented by the following formula (10) can be obtained. [Chemical formula] In the formula, R, A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 have the above meanings.

[0040] The complex (C') can advantageously catalyze the hydrosilylation reaction of the unsaturated compound (A) and the compound (B) containing at least one hydrosilyl functional group.

[0041] According to the first embodiment, compound (C) and (D) can be mixed before the hydrosilylation reaction, and the complex (C') can be optionally separated and purified before being used in the hydrosilylation reaction of compound (A) and compound (B).

[0042] According to the second embodiment, compound (D) can be introduced into the reaction medium together with reactants (A) and (B) and compound (C). Then, in-situ complex formation is possible during the hydrosilylation reaction.

[0043] During the implementation of the hydrosilylation method according to the present invention, the molar ratio of compound (D) to the cobalt element provided by compound (C) may be 0.5 to 4, preferably 0.8 to 3.5, and more preferably 1.5 to 3.

[0044] The hydrosilylation method according to the present invention is carried out in the presence of a compound (E) of the following formula (3): R’-OH (3) In the formula, R’ represents a hydrogen atom, or R’ is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, and a group of the formula Si(A 11 )3 (where each A 11 is independently selected from alkyl groups having 1 to 8 carbon atoms).) selected from the group consisting of silyl groups.

[0045] According to the first embodiment, R’ represents a hydrogen atom. At this time, the compound (E) is water.

[0046] Surprisingly, it has been demonstrated that the above hydrosilylation reaction using the cobalt catalyst can be carried out even in the presence of water. By adding a controlled amount of water, it is also possible to achieve better performance with respect to the conversion rate and selectivity of the reaction.

[0047] Furthermore, it has been found that water may be replaced with alcohol or silanol. According to the second embodiment, R’ is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, and a group of the formula Si(A 11 )3 (where each A 11 is independently selected from alkyl groups having 1 to 8 carbon atoms).) selected from the group consisting of silyl groups. Preferably, R’ can be selected from the group consisting of methyl, ethyl, isopropyl, t-butyl, phenyl, benzyl, trimethylsilyl, triethylsilyl, triisopropylsilyl and tri-t-butylsilyl.

[0048] During the hydrosilylation reaction according to the present invention, compound (E) is preferably present in a molar ratio of (compound (E)) / (Co element provided by cobalt compound (C)) of 0.1 to 500, more preferably 0.5 to 100. This ratio can be adjusted according to the properties of compounds (A) and (B).

[0049] According to the first embodiment, the unsaturated compound (A) is not an organopolysiloxane. The unsaturated compound (A) preferably contains 2 to 40 carbon atoms, more preferably 2 to 12 carbon atoms, contains one or more alkene or alkyne unsaturations that are not part of an aromatic ring, may be substituted by one or more halogen atoms, and one or more carbon atoms may be substituted by a heteroatom, typically an oxygen atom, a nitrogen atom, or a silicon atom, and is selected from hydrocarbon compounds. According to this first embodiment, compound (E) is preferably present in a molar ratio of (compound (E)) / (Co element provided by cobalt compound (C)) of 0.1 to 100, preferably 0.1 to 50, and more preferably 0.5 to 15.

[0050] According to the second embodiment, the unsaturated compound (A) may be an organopolysiloxane compound containing one or more alkene functional groups, preferably at least two alkene functional groups. According to this embodiment, compound (E) is preferably present in a molar ratio of (compound (E)) / (Co element provided by cobalt compound (C)) of 0.5 to 300, preferably 5 to 100.

[0051] Further, the present invention relates to at least one unsaturated compound (A) containing at least one functional group selected from an alkene functional group and an alkyne functional group, a compound (B) containing at least one hydrosilyl functional group, and a cobalt compound (C) of the following formula (1): [Co(N(SiR3)2) x y (1) (wherein, · The symbol R may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, · x = 1, 2 or 3,​ ·y = 1 or 2.) and Compound (D) of the following formula (2): [Chemical formula] (In the formula, ·A 1 , A 2 , A 3 and A 4 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, a halogen, and the formula OA 9 (wherein A 9 is an alkyl group having 1 to 8 carbon atoms).) selected from alkoxy groups, ·A 5 and A 6 are each independently selected from a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an arylalkyl group having 7 to 24 carbon atoms, ·A 7 and A 8 are each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, and the formula OA 10 (wherein A 10 is an alkyl group having 1 to 8 carbon atoms).) selected from alkoxy groups.) and Compound (E) of the following formula (3): R’-OH (3) (wherein R’ represents a hydrogen atom, or R’ is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, and the formula Si(A 11 )3(wherein each A 11is independently selected from alkyl groups having 1 to 8 carbon atoms each. selected from the group consisting of silyl groups of)).) and It also relates to a composition containing

[0052] In the hydrosilylation method according to the present invention, the unsaturated compound (A) used is a compound containing at least 1 alkene or alkyne unsaturation that is not part of an aromatic ring. The unsaturated compound (A) contains at least 1 functional group selected from alkene functional groups and alkyne functional groups, preferably at least 1 functional group selected from alkene functional groups. This can be selected from those known to those skilled in the art and those that do not contain reactive chemical functional groups that may interfere with and actually inhibit the hydrosilylation reaction.

[0053] According to one embodiment, the unsaturated compound (A) contains 1 or more alkene functional groups and 2 to 40 carbon atoms. According to another embodiment, the unsaturated compound (A) contains 1 or more alkyne functional groups and 2 to 40 carbon atoms. Preferably, the unsaturated compound (A) contains 2 to 40 carbon atoms, more preferably 2 to 12 carbon atoms, contains 1 or more alkenes or alkynes that are not part of an aromatic ring, may be substituted with 1 or more halogen atoms, and 1 or more carbon atoms may be substituted with heteroatoms, typically oxygen atoms, nitrogen atoms or silicon atoms, and can be selected from hydrocarbon compounds.

[0054] The unsaturated compound (A) is preferably selected from the group consisting of acetylene, acrylates and methacrylates of C1-C4 alkyl, acrylic acid or methacrylic acid, alkenes, preferably octene, more preferably 1-octene, allyl alcohol, allyl amine, allyl glycidyl ether, N-allyl piperidine, sterically hindered N-allyl piperidine derivatives, styrene, preferably α-methylstyrene, 1,2-epoxy-4-vinylcyclohexane, chlorinated alkenes, preferably allyl chloride, fluorinated alkenes, preferably 4,4,5,5,6,6,7,7,7-nonafluoro-1-heptene.

[0055] The unsaturated compound (A) can be a disiloxane such as vinylpentamethyldisiloxane or divinyltetramethyldisiloxane.

[0056] The unsaturated compound (A) can be selected from compounds containing several alkene functional groups, preferably 2 or 3 alkene functional groups. Particularly preferably, the compound (A) is selected from the following compounds. [Chemical formula]

[0057] According to a preferred embodiment, the unsaturated compound (A) can be an organopolysiloxane compound containing one or more alkene functional groups, preferably at least 2 alkene functional groups. The hydrosilylation reaction of alkenes is one of the important reactions in silicone chemistry. This not only crosslinks an organopolysiloxane having an SiH functional group and an organopolysiloxane having an alkenyl functional group to form a network and imparts mechanical properties to the material, but also enables the functionalization of the organopolysiloxane having an SiH functional group to modify its physical and chemical properties. The organopolysiloxane compound is particularly · At least 2 siloxyl units of the following formula: Vi a U b SiO (4-a-b) / 2 (In the formula, Vi is a C2-C6 alkenyl group, preferably a vinyl group, U is a monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably selected from an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group or a propyl group, a cycloalkyl group having 3 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms, a = 1, 2 or 3, preferably a = 1 or 2; b = 0, 1 or 2; and the sum a + b = 1, 2 or 3.) and · Optionally, a unit of the following formula: U c SiO (4-c) / 2 (wherein U has the same meaning as above, and c = 0, 1, 2, or 3), and is composed of.

[0058] In the above formula, when a plurality of U groups are present, they may be the same as or different from each other.

[0059] The compound containing one or more alkene functional groups is composed of "D" and "D 2 / 2 , ViUSiO 2 / 2 and U2SiO 2 / 2 selected from the group consisting of siloxyl units, and the terminal "M" and "M Vi " siloxyl units selected from the group consisting of ViU2SiO 1 / 2 , Vi2USiO 1 / 2 and U3SiO 1 / 2 siloxyl units, and can have a linear structure essentially consisting of. The symbols Vi and U are as defined above. Vi Examples of the terminal "M" and "M

[0060] " siloxyl units include trimethylsiloxy group, dimethylphenylsiloxy group, dimethylvinylsiloxy group, or dimethylhexenylsiloxy group. Vi Examples of the "D" and "D

[0061] " siloxyl units include dimethylsiloxy group, methylphenylsiloxy group, methylvinylsiloxy group, methylbutenylsiloxy group, methylhexenylsiloxy group, methyldecenylsiloxy group, or methyldecadienylsiloxy group. Vi Examples of the linear organopolysiloxane that can be an organopolysiloxane compound containing one or more alkene functional groups according to the present invention are as follows:

[0062] · Dimethylvinylsilyl-terminated poly(dimethylsiloxane); · Dimethylvinylsilyl-terminated poly(dimethylsiloxane-co-methylphenylsiloxane); · · Dimethylvinylsilyl-terminated poly(dimethylsiloxane-co-methylvinylsiloxane); · Trimethylsilyl-terminated poly(dimethylsiloxane-co-methylvinylsiloxane); and · Cyclic poly(methylvinylsiloxane).

[0063] In the most preferred embodiment, the organopolysiloxane compound containing one or more alkene functional groups contains terminal dimethylvinylsilyl units. More preferably, the organopolysiloxane compound containing one or more alkene functional groups is dimethylvinylsilyl-terminated poly(dimethylsiloxane).

[0064] The viscosity of the silicone oil is generally from 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 dynamic viscosity of from 20 mPa·s to 100,000 mPa·s at 25°C, preferably from 20 mPa·s to 80,000 mPa·s at 25°C, more preferably from 100 mPa·s to 50,000 mPa·s.

[0065] Optionally, the organopolysiloxane compound containing one or more alkene functional groups may further contain "T" (USiO 3 / 2 ) siloxyl units and / or "Q" (SiO 4 / 2 ) siloxyl units. The U symbol is as described above. And the organopolysiloxane compound containing one or more alkene functional groups has a branched structure.

[0066] Examples of the branched organopolysiloxane, also called a resin, which is an organopolysiloxane compound containing one or more alkene functional groups according to the present invention are as follows: · MD Vi Q, where the vinyl group is contained in the D unit, · MD Vi TQ, where the vinyl group is contained in the D unit, · MM Vi Q, where the vinyl group is contained in a part of the M unit, · MMVi TQ, where the vinyl group is included as part of the M unit, ·MM Vi DD Vi Q, where the vinyl group is included as part of the M unit and the D unit, · and mixtures thereof; where M Vi = a siloxyl unit of formula (U)2(vinyl)SiO 1 / 2 D Vi = a siloxyl unit of formula (U)(vinyl)SiO 2 / 2 T = a siloxyl unit of formula (U)SiO 3 / 2 Q = a siloxyl unit of formula SiO 4 / 2 M = a siloxyl unit of formula (U)3SiO 1 / 2 D = a siloxyl unit of formula (U)2SiO 2 / 2 and D = a siloxyl unit of formula (U)2SiO, where U is as described above.

[0067] Preferably, the organopolysiloxane compound containing one or more alkene functional groups has a weight content of alkenyl units of 0.001 wt% to 30 wt%, preferably 0.01 wt% to 10 wt%, more preferably 0.02 wt% to 5 wt%.

[0068] The unsaturated compound (A) reacts with the compound (B) containing at least one hydrosilyl functional group according to the present invention.

[0069] According to one embodiment, the compound (B) containing at least one hydrosilyl functional group is a silane or polysilane compound containing at least one hydrogen atom bonded to a silicon atom. The "silane" compound means, in the present invention, a compound containing a silicon atom bonded to four hydrogen atoms or organic substituents. The "polysilane" compound means, in the present invention, a compound having at least one ≡Si-Si≡ unit. Among the silane compounds, the compound (B) containing at least one hydrosilyl functional group can be phenylsilane, or mono-, di- or trialkylsilane, such as triethylsilane.

[0070] According to another embodiment, 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, also known as an organohydropolysiloxane. Advantageously, the organohydropolysiloxane is · at least two siloxyl units of the following formula: H d U e SiO (4-d-e) / 2 (wherein, U is a monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group or a propyl group, a cycloalkyl group having 3 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms, d = 1, 2 or 3, preferably d = 1 or 2; e = 0, 1 or 2; and d + e = 1, 2 or 3.) and, · Optionally, a unit of the following formula: U f SiO (4-f) / 2 (wherein U has the same meaning as above and f = 0, 1, 2 or 3.) and can be an organopolysiloxane composed of

[0071] In the above formula, when several U groups are present, they may be the same or different from each other. Preferably, U can represent a monovalent group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms, which may be substituted with at least one halogen atom such as chlorine or fluorine. U can preferably be selected from the group consisting of methyl, ethyl, propyl, 3,3,3-trifluoropropyl, xylyl, tolyl and phenyl.

[0072] In the above formula, the symbol d is preferably equal to 1.

[0073] The organohydro polysiloxane can have a linear, branched or cyclic structure. The degree of polymerization is preferably 2 or more and generally 5000 or less.

[0074] In the case of linear polymers, these are siloxyl units selected from the units of the following formula D: U2SiO 2 / 2 or D’: UHSiO 2 / 2 and terminal siloxyl units selected from the units of the following formula M: U3SiO 1 / 2 or M’: U2HSiO 1 / 2 and essentially consist of, where U has the same meaning as above.

[0075] Examples of the organohydro polysiloxane which can be the compound (B) containing at least one hydrosilyl functional group according to the present invention are as follows: · Hydrodimethylsilyl-terminated poly(dimethylsiloxane); · Trimethylsilyl-terminated poly(dimethylsiloxane-co-methylhydrogensiloxane); · Hydrodimethylsilyl-terminated poly(dimethylsiloxane-co-methylhydrogensiloxane); · Trimethylsilyl-terminated poly(methylhydrogensiloxane); and · Cyclic poly(methylhydrogensiloxane).

[0076] When the organohydro polysiloxane has a branched structure, it is preferably selected from the group consisting of silicone resins of the following formula: · M’Q, where the hydrogen atom bonded to the silicon atom is held by the M group, · MM’Q, where the hydrogen atom bonded to the silicon atom is held by a part of the M unit, · MD’Q, where the hydrogen atom bonded to the silicon atom is held by the D group, · MDD’Q, where the hydrogen atom bonded to the silicon atom is held by a part of the D group, · MM’TQ, where the hydrogen atom bonded to the silicon atom is held by a part of the M unit, ·MM’DD’Q, where the hydrogen atoms bonded to silicon atoms are held by part of the M unit and the D unit. · and mixtures thereof Here, M, M’, D and D’ are as defined above, T: the siloxyl unit of the formula USiO 3 / 2 and Q: the siloxyl unit of the formula SiO 4 / 2 where U has the same meaning as above.

[0077] Preferably, the organohydrogenpolysiloxane compound has a Si-H hydrosilyl functional group content of 0.2% to 91% by weight, more preferably 3% to 80% by weight, and even more preferably 15% to 70% by weight.

[0078] According to a specific embodiment of the present invention, the unsaturated compound (A) and the compound (B) containing at least one hydrosilyl functional group can first be the same compound containing at least one ketone functional group, one aldehyde functional group, one alkene functional group and / or one alkyne functional group, and second, at least one silicon atom and at least one hydrogen atom bonded to the silicon atom. This compound can be described as "bifunctional" and can react itself by a hydrosilylation reaction. Therefore, the present invention can also relate to a method for hydrosilylating the bifunctional compound itself. The bifunctional compound first contains at least one functional group selected from the group consisting of a ketone functional group, an aldehyde functional group, an alkene functional group and an alkyne functional group (preferably at least one alkene functional group and / or at least one alkyne functional group), and second, at least one silicon atom and at least one hydrogen atom bonded to the silicon atom. The method is catalyzed by a cobalt compound (C) in the presence of a compound (D) and a compound (E) as described above.

[0079] Examples of organopolysiloxanes that can be bifunctional compounds are as follows: · Dimethylvinylsilyl-terminated poly(dimethylsiloxane-co-hydroxymethylsiloxane-co-vinylmethylsiloxane), · Dimethylhydrosilyl-terminated poly(dimethylsiloxane-co-hydroxymethylsiloxane-co-vinylmethylsiloxane); and · Trimethylsilyl-terminated poly(dimethylsiloxane-co-hydroxymethylsiloxane-co-(propyl glycidyl ether)methylsiloxane).

[0080] Regarding the use of an unsaturated compound (A) and a compound (B) containing at least one hydrosilyl functional group, those skilled in the art will understand that this also means the use of a bifunctional compound.

[0081] The amounts of compound (A) and compound (B) can be controlled such that the molar ratio of the hydrosilyl functional group of compound (B) to the alkene functional group and alkyne functional group of compound (A) is preferably 1:10 to 10:1, more preferably 1:5 to 5:1, and even more preferably 1:3 to 3:1.

[0082] The hydrosilylation reaction can be carried out in a solvent or in the absence of a solvent. In another embodiment, one of the reactants, for example, the unsaturated compound (A), can act as a solvent. Suitable solvents are solvents miscible with compound (B). 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, more preferably 50°C to 140°C, and even more preferably 50°C to 100°C.

[0083] According to a preferred embodiment of the present invention, the compounds (A) and (B) used are selected from the organopolysiloxanes defined above. In this case, a three-dimensional network is formed, and as a result, the composition cures. The crosslinking is accompanied by a gentle physical change in the medium constituting the composition. As a result, using the method according to the present invention, elastomers, gels, foams, etc. can be obtained. 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 a composition containing an organopolysiloxane having at least two unsaturated bonds and an organopolysiloxane having at least three hydrosilyl units. The crosslinked silicone material can be, for example, an elastomer, a gel or a foam.

[0084] According to this preferred embodiment of the method according to the present invention, where the compounds (A) and (B) are selected from organopolysiloxanes as defined above, it is possible to use conventional functional additives in the silicone composition. Examples of conventional functional additives can include the following: · Fillers, · Adhesion promoters, · Inhibitors or retarders of the hydrosilylation reaction, · Adhesion regulators, · Silicone resins, · Consistency improvers, · Pigments · Heat-resistant additives, oil-resistant additives, fire-resistant additives, such as metal oxides, etc.

[0085] Other details or advantages of the present invention will become more clearly apparent in light of the examples shown below for illustrative purposes only.

Examples

[0086] All experiments on compounds sensitive to air and compounds sensitive to moisture were carried out under an inert atmosphere of dry argon and inside a glove box. Before use, the solvents and reactants used were purified and degassed, dried over molecular sieves and stored.

[0087] Example 1: Co[N(SiMe 3 ) 3 ] 2 Synthesis of Cobalt(II) Bisamide Complex (COBAM) 1.0830 g (8.34×10 -3 mol) of cobalt chloride CoCl2 and 2.7895 g (1.67×10 -2 mol) of lithium bis(trimethylsilyl)amide LiN(SiMe3)2 were weighed in a 200 ml Schlenk tube in a glove box. Added to a tube immersed in an ice bath with 100 ml of Et2O, and the suspension was stirred at 0 °C for 10 hours. The solution showed a dark green color and a white / grey precipitate was formed. The solvent was evaporated and the complex was extracted 3 times with 30 ml of pentane. After evaporating the pentane, a viscous green oil was obtained. Then, this oil was sublimed at 80 °C under high vacuum (10 -7 mbar) to obtain a brownish powder. Yield = 70%.

[0088] Example 2: Synthesis of Cobalt(II) Bisamide + Ligand Complex (COBAM+PN)

Chemical formula

[0089] Examples 3-10: Functionalization Tests Under an argon inert atmosphere, inside a glove box, the required mass of the cobalt(II) bisamide complex (COBAM) obtained as described in Example 1 was weighed and introduced into a dry, sealed flask. The required mass of the PN ligand was weighed and introduced into the flask. 0.3 g of dodecane was added and the medium was placed under stirring to dissolve the precatalyst. Next, the required mass of the unsaturated compound (A) was introduced, followed by the introduction of the required mass of compound (B). Under an argon stream, using a micropipette, the required volume of compound (E) was introduced. Thereafter, the reaction medium was placed under stirring for 5 minutes and placed into a small metal barrel preheated to 75 °C (t = 0).

[0090] To determine the conversion rate and selectivity, the reaction medium was quantitatively analyzed by gas chromatography.

[0091] For all of Examples 3 to 15, the compound (B) used was 1,1,1,3,5,5,5 - heptamethyl - 3 - hydrotrisiloxane (hereinafter, "MD'M"). The SiH / SiVi molar ratio = 1. The catalyst amount (COBAM) = 0.5 mol% (mol% of cobalt element provided by the catalyst relative to the number of moles of vinyl radicals bonded to silicon provided by compound (B)).

[0092]

Table 1

[0093] Examples 16-26: Crosslinking Tests The required mass of cobalt(II) bisamide complex (COBAM) was weighed in a glove box under an inert atmosphere of argon and introduced into a dry, sealed flask. The required mass of the PN ligand was weighed and introduced into the flask. Next, the organopolysiloxane was introduced in the following order. First, the unsaturated organopolysiloxane (A) was injected. Next, the medium was stirred to dissolve the complex (COBAM). Finally, the hydrogenated organopolysiloxane (B) was added. Under an argon stream, using a micropipette, the required volume of compound (E) was introduced. Thereafter, the reaction medium was stirred for 5 minutes and placed in a small metal barrel preheated to 90 °C (t = 0).

[0094] The gel time of the crosslinking test was qualitatively measured by the stirring stop time (SST). This SST is associated with a significant increase in viscosity such that the medium can no longer be stirred (corresponding to a viscosity of approximately 1000 mPa·s).

[0095] For all of Examples 16 - 26, the SiH / SiVi molar ratio = 2. The amount of catalyst (COBAM) = 1 mol% (mole percentage of cobalt element provided by the catalyst relative to the number of moles of vinyl groups bonded to silicon provided by compound (B)).

[0096] A1: Dimethylvinylsilyl-terminated poly(dimethylsiloxane), viscosity at 25 °C: approximately 100 mPa·s, vinyl group content: approximately 1.08 wt%.

[0097] B1: Trimethylsilyl-terminated poly(methylhydrosiloxane), viscosity at 25 °C: approximately 20 mPa·s, SiH group content: approximately 44.5 wt%.

[0098] B2: Hydrodimethylsilyl-terminated and trimethylsilyl-terminated poly(dimethylsiloxane-co-methylhydrosiloxane), viscosity at 25 °C: approximately 20 mPa·s, SiH group content: approximately 20 wt%.

[0099] [Table 2]

Claims

1. A method for hydrosilylating an unsaturated compound A containing at least one functional group selected from an alkene functional group and an alkyne functional group with a compound B containing at least one hydrosilyl functional group, wherein the method comprises the unsaturated compound A, the compound B, and a cobalt compound C of the following formula (1): [Co(N(SiR 3 ) 2 ) x ] y (1) (wherein, - The symbol R may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, - x = 1, 2 or 3, - y = 1 or 2.) and a compound D of the following formula (2): 【Chemical Formula 1】 (wherein, - A 1 、A 2 、A 3 and A 4 are each independently selected from a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, a halogen, and an alkoxy group of the formula OA 9 (wherein A 9 is an alkyl group having 1 to 8 carbon atoms.) - A 5 and A 6 are each independently selected from a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an arylalkyl group having 7 to 24 carbon atoms, - A 7 and A 8is, independently of one another, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, and the formula OA 10 wherein A 10 is an alkyl group having 1 to 8 carbon atoms.), and is selected from the group consisting of alkoxy groups of the formula: Compound E of the following formula (3): R'-OH (3) (wherein R'represents a hydrogen atom, or R' is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, and the formula Si(A 11 )) 3 where each A 11 is independently selected from alkyl groups having 1 to 8 carbon atoms.) and is selected from the group consisting of silyl groups of the formula: and contacting the same. A method comprising the step of

2. The method according to claim 1, wherein the compound E is water.

3. The compound E is of the following formula (3): R'-OH (3) (wherein R' is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, and the formula Si(A 11 )) 3 where each A 11 is independently selected from alkyl groups having 1 to 8 carbon atoms.) and is selected from the group consisting of silyl groups of the formula: The method according to claim 1, which is an alcohol or silanol of the formula:

4. The method according to any one of claims 1 to 3, wherein the compound E is present in a molar ratio of (compound E) / (Co element provided by the cobalt compound C) of 0.1 to 500.

5. The cobalt compound C is represented by the following formula: [Co(N(Si(CH 3 ) 3 ) 2 ) 2 ] y (wherein y is equal to 1 or 2). The method according to any one of claims 1 to 4, represented by

6. The compound D is represented by the following formula (2): 【Chemical formula 2】 (wherein - A 1 , A 2 , A 3 and A 4 are hydrogen atoms, - A 5 and A 6 are hydrogen atoms, - A 7 and A 8 are independently selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, and an alkoxy group of the formula OA 10 (where A 10 is an alkyl group having 1 to 8 carbon atoms).) The method according to any one of claims 1 to 5, represented by

7. The unsaturated compound A is not an organopolysiloxane, and contains 2 to 40 carbon atoms, contains one or more alkene or alkyne unsaturations that are not part of an aromatic ring, may be substituted by one or more halogen atoms, and one or more carbon atoms may be substituted by a heteroatom, typically an oxygen atom, a nitrogen atom or a silicon atom, and is selected from hydrocarbon compounds, the method according to any one of claims 1 to 6.

8. 8. The method of claim 7, wherein the compound E is present in a (compound E) / (element Co provided by cobalt compound C) molar ratio of 0.1-100.

9. The method according to any one of claims 1 to 6, wherein the unsaturated compound A is an organopolysiloxane compound containing one or more alkene functional groups.

10. 10. The method of claim 9, wherein the compound E is present in a (compound E) / (element Co provided by cobalt compound C) molar ratio of 0.5 to 300.

11. At least one unsaturated compound A containing at least one functional group selected from an alkene functional group and an alkyne functional group, a compound B containing at least one hydrosilyl functional group, and a cobalt compound C of the following formula (1): [Co(N(SiR 3 ) 2 ) x ] y (1) (In the formula, the symbols R, which may be identical or different, represent a hydrogen atom or a hydrocarbon radical having 1 to 12 carbon atoms, x=1, 2 or 3, y=1 or 2; and Compound D of the following formula (2): [C3] (In the formula, ・A 1 , A 2 , A 3 and A 4 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, a halogen, and a group of the formula OA 9 (Here, A 9 is an alkyl group having 1 to 8 carbon atoms; ・A 5 and A 6are, independently of one another, selected from a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an arylalkyl group having 7 to 24 carbon atoms, - A 7 and A 8 are, independently of one another, selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, and an alkoxy group of the formula OA 10 (wherein A 10 is an alkyl group having 1 to 8 carbon atoms.)), and a compound E of the following formula (3): R'-OH (3) (wherein R' represents a hydrogen atom, or R' is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, and a group of the formula Si(A 11 ) 3 (wherein each A 11 is, independently of one another, selected from alkyl groups having 1 to 8 carbon atoms.)), and a composition containing

12. The composition according to claim 11, wherein the compound E is present in a molar ratio of (compound E) / (Co element provided by the cobalt compound C) of 0.1 to 500.

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