Curable silicone composition, preparation method and curable method thereof, silicone cured product and preparation method thereof, and [2+2 +2] cycloaddition reaction product and preparation method thereof

Abstract

The present invention provides a curable silicone composition characterized by comprising: (A) 100 parts by mass of an organopolysiloxane having at least one alkynyl group or nitrile group in one molecule; and an effective amount of (B) a transition metal compound, a typical metal compound, or a combination thereof capable of catalyzing the [2 + 2 + 2] cycloaddition reaction. Thus, a curable silicone composition is provided which does not require special temperature management during storage and transportation, can reduce environmental burden, and is not susceptible to the influence of a substance that suppresses curing of a conventionally known addition-curable silicone composition.

Description

Technical Field

[0001] The present invention relates to a curable silicone composition, a silicone cured product, a method for preparing the curable silicone composition, a method for preparing the silicone cured product, a method for curing the curable silicone composition, a [2+2+2] cycloaddition reaction product, and a method for preparing the [2+2+2] cycloaddition reaction product. Background Art

[0002] Since curable silicone compositions form silicone gels, silicone rubbers, hard coatings, etc. with excellent electrical properties, cold resistance, heat resistance, and chemical stability after curing, they are widely used as sealants, fillers or coating agents for electrical and electronic components and semiconductor elements, and insulating coating protective agents for optical semiconductors. In addition, by blending various fillers, the strength of the composition can be increased or heat resistance can be imparted. In addition, they are also used as heat dissipation materials and conductive materials for electronic components such as semiconductor elements and LED (light emitting diode) substrates. In recent years, against the backdrop of the growing momentum for carbon neutrality, a curable silicone composition that can reduce environmental burden without the need for special temperature management during storage and transportation is being sought.

[0003] The curing forms of curable silicone compositions can be roughly divided into three types: "addition curing", "condensation curing" and "peroxide curing". Addition curing silicone compositions generally lack storage properties at room temperature and must be stored and transported in a frozen or refrigerated state. Although a two-liquid curing type in which the catalyst component and the crosslinking agent component are separated can be stored and transported at room temperature, a device must be introduced to quantitatively and uniformly mix the two liquids. In addition, although the catalyst component can be stored and transported at room temperature under light-shielded conditions by using a UV (ultraviolet) active catalyst instead of a general temperature-responsive catalyst, a device for irradiating UV must be introduced to cure it. In addition, regardless of the single-liquid or two-liquid curing type, temperature-responsive or UV-active catalyst metal, the catalyst component is deactivated by amine compounds contained in cutting oil and epoxy molding materials, etc., so poor curing sometimes occurs.

[0004] Since condensation-curable silicone compositions are cured by moisture in the air, they can be stored and transported at room temperature as long as they are shielded from moisture. However, low-boiling-point components are generated during the curing reaction, so they are not preferred from the perspective of environmental burden. In addition, the curing system that uses moisture in the air to cure also has a technical problem of poor deep curability.

[0005] Although peroxide-curable silicone compositions can be stored and transported at room temperature by selecting an appropriate peroxide catalyst, they have a technical problem of being inhibited from curing by oxygen in the air.

[0006] When curing properties and handling properties are considered together, a one-component addition-curing silicone composition is considered to be the most suitable, but as mentioned above, it is difficult to store and transport at room temperature. As a method for improving the storage properties of a one-component addition-curing silicone composition at room temperature, there is a method of adding an appropriate amount of an addition curing reaction controller such as acetylene alcohol (Patent Document 1). However, when the above-mentioned addition curing reaction controller is added to a degree that allows storage and transportation at room temperature, there is also a problem that the curing reaction does not proceed sufficiently in the subsequent curing step of the addition-curing silicone composition, resulting in poor curing.

[0007] As another method, a microcapsule structure formed by embedding a catalyst component in a polymer compound is considered to be more effective (e.g., Patent Documents 2 and 3). However, the catalyst component embedded in the microcapsule structure has a slow diffusion rate in the composition and is difficult to induce an addition curing reaction. Therefore, in the curing step, there are cases where the curing reaction does not proceed sufficiently and causes poor curing.

[0008] Addition-curing silicone compositions sometimes contain compounds having a carbon-carbon triple bond as a curing retarder (reaction control agent). The curing retarder not only controls the reaction rate of the addition reaction (hydrosilylation) to extend the pot life of the addition-curing silicone composition, but also has the function of preventing the following situation: due to the silicone composition curing too quickly, part of it begins to cure during processing. On the other hand, in Patent Document 4, a silicone compound having a carbon-carbon triple bond is polymerized in the presence of a catalyst to obtain a substituted polyacetylene compound. In addition to polymerizing to obtain a linear polymer as described above, a compound having a carbon-carbon triple bond can also undergo a cycloaddition reaction to obtain a polymer having a multi-branched structure, that is, a hyperbranched polymer (Patent Documents 5 and 6). In addition, Non-Patent Document 1 states that alkynes and nitriles undergo a [2+2+2] cycloaddition reaction to obtain cyclic compounds such as pyridine.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Laid-Open No. 4-46962

[0012] Patent Document 2: Japanese Patent Application Laid-Open No. 11-236508

[0013] Patent Document 3: Japanese Patent Application Publication No. 2014-024986

[0014] Patent Document 4: Japanese Patent Application Laid-Open No. 61-268745

[0015] Patent Document 5: U.S. Patent Application Publication No. 2003 / 225232

[0016] Patent Document 6: Japanese Patent Application Publication No. 2019-206676

[0017] Non-patent literature

[0018] Non-patent document 1: Chem. Rev. 2003, 103, 3787-3801 Summary of the invention

[0019] 1. Technical issues to be resolved

[0020] As mentioned above, various studies have been conducted on the curing of curable silicone compositions, and further improvements are being sought from the perspectives of reducing environmental burden and processability. When considering both curability and handling properties, single-component addition-curable silicone compositions are more suitable, but even so, they still cannot achieve both room temperature storage and good curing reaction.

[0021] That is, conventional addition-curable silicone compositions have the following problems: since temperature control is required, it is difficult to reduce environmental burdens, and they are easily affected by curing inhibitors such as amine compounds contained in cutting oils and epoxy molding materials.

[0022] Furthermore, although compounds having a carbon-carbon triple bond undergo addition reactions to form polymers, a [2+2+2] cycloaddition reaction of organopolysiloxanes having a carbon-carbon triple bond has not been known so far.

[0023] Therefore, the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a curable silicone composition that does not require special temperature management during storage and transportation and can reduce environmental burden, and is not easily affected by substances that inhibit curing of conventionally known addition-curable silicone compositions.

[0024] Another object of the present invention is to provide a novel substance, namely, a [2+2+2] cycloaddition reaction product of an organopolysiloxane having at least one alkynyl group or nitrile group in one molecule, and a method for preparing the same.

[0025] (II) Technical solution

[0026] In order to solve the above technical problems, the present invention provides a curable silicone composition, characterized in that it comprises:

[0027] 100 parts by mass of (A) an organopolysiloxane having at least one acetylenic group or nitrile group in one molecule; and

[0028] An effective amount of (B) a transition metal compound, a typical metal compound or a combination thereof capable of catalyzing a [2+2+2] cycloaddition reaction.

[0029] Such a curable silicone composition does not require special temperature management during storage and transportation, and can reduce environmental burden. In addition, the composition is less susceptible to substances that inhibit curing of conventionally known addition-curable silicone compositions.

[0030] In the present invention, it is preferred that the kinematic viscosity of the component (A) at 25°C is 1 to 20,000,000 mm 2 / s of organopolysiloxane.

[0031] If the above kinematic viscosity is 1 mm 2 / s or more, the physical properties of the curable silicone composition are good. If it is 20,000,000 mm 2 / s or less, the spreadability of the curable silicone composition is sufficient.

[0032] In the present invention, the component (A) is preferably an organopolysiloxane having at least one acetylene group in one molecule, and the component (A) is more preferably an organopolysiloxane having at least one ethynyl group in one molecule.

[0033] The component (A) is preferably such an organopolysiloxane.

[0034] In the present invention, it is preferred that the component (B) is a transition metal complex capable of catalyzing a [2+2+2] cycloaddition reaction.

[0035] As the component (B), such a transition metal complex is suitable as a catalyst for the [2+2+2] cycloaddition reaction.

[0036] In the present invention, it is preferred that (C) at least one inorganic filler or organic filler is further contained, and the amount of the component (C) is 0.1 to 5,000 parts by mass based on 100 parts by mass of the component (A).

[0037] Such component (C) can impart various properties such as thermal conductivity, heat resistance, reinforcement, electrical conductivity, and designability to the curable silicone composition of the present invention. When the blending amount is within the above range, the viscosity is not too high and the composition can be easily handled, resulting in a uniform composition.

[0038] In this case, the component (C) is preferably a filler composed of one or more materials selected from the group consisting of metals, metal oxides, metal hydroxides, metal nitrides, metal carbides, carbon allotropes, resins, dyes, and pigments.

[0039] By selecting such a material for the filler, it is possible to impart properties such as thermal conductivity, heat resistance, reinforcement, electrical conductivity, smoothness, and designability to the composition.

[0040] In addition, the present invention provides a cured organosilicon product obtained by curing the curable organosilicon composition.

[0041] The organosilicon cured product of the present invention has excellent electrical properties, cold resistance, heat resistance and chemical stability, and can be widely used as a sealant, filler or coating agent for electrical and electronic components and semiconductor elements, and an insulating coating protective material for optical semiconductors in the form of silicone gel, silicone rubber, hard coating film, etc. In addition, by containing various fillers, the strength can be improved or heat resistance can be imparted. In addition, it is also used as a heat dissipation material and conductive material for electronic components such as semiconductor elements and LED substrates.

[0042] In addition, the present invention provides a method for preparing a curable silicone composition, characterized in that 100 parts by mass of (A) an organic polysiloxane having at least one acetylenic group or nitrile group in one molecule and an effective amount of (B) a transition metal compound, a typical metal compound or a combination thereof capable of catalyzing a [2+2+2] cycloaddition reaction are mixed.

[0043] According to the method for producing a curable silicone composition of the present invention, the curable silicone composition can be produced efficiently.

[0044] In addition, the present invention provides a method for preparing an organic silicon cured product, characterized in that it comprises: a step of mixing 100 parts by mass of (A) an organic polysiloxane having at least one acetylenic group or nitrile group in one molecule, and an effective amount of (B) a transition metal compound, a typical metal compound or a combination thereof capable of catalyzing a [2+2+2] cycloaddition reaction; and a step of curing the obtained mixture.

[0045] In addition, the present invention provides a method for preparing a curable silicone composition, characterized in that a mixture is cured, wherein the mixture comprises:

[0046] (A) an organopolysiloxane having at least one acetylenic group or nitrile group in one molecule; and

[0047] An effective amount of (B) a transition metal compound, a typical metal compound or a combination thereof capable of catalyzing a [2+2+2] cycloaddition reaction.

[0048] By doing so, the curable silicone composition can be suitably cured, and a silicone cured product can be efficiently produced.

[0049] The present invention also provides a [2+2+2] cycloaddition reaction product of an organopolysiloxane having at least one alkynyl group or nitrile group in one molecule.

[0050] The [2+2+2] cycloaddition reaction product of the present invention can reduce environmental burden because it does not require special temperature management during storage and transportation, and is not easily affected by substances that inhibit curing, so it is excellent as a main component of a curable silicone composition.

[0051] In addition, the present invention provides a method for preparing a [2+2+2] cycloaddition reaction product, characterized in that (B) a transition metal compound, a typical metal compound or a combination thereof capable of catalyzing the [2+2+2] cycloaddition reaction is used to cause (A) an organic polysiloxane having at least one alkynyl group or nitrile group in one molecule to undergo a [2+2+2] cycloaddition reaction, thereby obtaining a product.

[0052] According to the method for producing a [2+2+2] cycloaddition reaction product of the present invention, a [2+2+2] cycloaddition reaction product can be efficiently produced from an organopolysiloxane having an alkynyl group or a nitrile group.

[0053] (III) Beneficial effects

[0054] The curable silicone composition of the present invention utilizes an organopolysiloxane having at least one acetylenic group or nitrile group in one molecule and a transition metal compound, a typical metal compound, or a combination thereof that can catalyze a [2+2+2] cycloaddition reaction, thereby having the following advantages: it can be stored at room temperature and transported at room temperature, and is not easily affected by substances that inhibit the curing of conventionally known addition-curable silicone compositions. As a result, no special temperature management is required during storage and transportation, and the environmental burden can be reduced. Even if there are substances that inhibit the curing of conventionally known addition-curable silicone compositions, the curing reaction will not be inhibited in the present invention. Therefore, the curable silicone composition of the present invention can also be used in locations where cutting oils and epoxy molding materials containing curing-inhibiting substances such as amine compounds are used. DETAILED DESCRIPTION

[0055] As described above, there has been a demand for the development of an addition-curable silicone composition that does not require special temperature management during storage and transportation and is less susceptible to substances that inhibit the curing of conventional addition-curable silicone compositions.

[0056] The inventors of the present application have conducted in-depth studies on the above-mentioned technical problems and found that if an organopolysiloxane having at least one acetylenic group or nitrile group in one molecule is combined with a catalyst active in the [2+2+2] cycloaddition reaction, the organopolysiloxane can be cured even in the presence of substances that inhibit the curing of conventional addition-curing silicone compositions, and no special temperature management is required during storage and transportation.

[0057] That is, the present invention is a curable silicone composition, characterized in that it comprises:

[0058] 100 parts by mass of (A) an organopolysiloxane having at least one acetylenic group or nitrile group in one molecule; and

[0059] An effective amount of (B) a transition metal compound, a typical metal compound or a combination thereof capable of catalyzing a [2+2+2] cycloaddition reaction.

[0060] The present invention will be described in detail below, but the present invention is not limited thereto.

[0061] The present invention relates to a curable silicone composition. Specifically, the present invention relates to a curable silicone composition that can be stored and transported at room temperature and is not easily affected by substances that inhibit the curing of conventional addition-curable silicone compositions.

[0062] [Curable silicone composition]

[0063] The curable silicone composition of the present invention is characterized in that it comprises: 100 parts by mass of (A) an organopolysiloxane having at least one acetylenic group or nitrile group in one molecule; and an effective amount of (B) a transition metal compound, a typical metal compound or a combination thereof capable of catalyzing a [2+2+2] cycloaddition reaction. The curable silicone composition comprises components (A) and (B), and may further comprise other components such as component (C) (inorganic filler or organic filler) and components for adjusting the strength and viscosity of the composition as described below as needed.

[0064] In the present invention, the organopolysiloxane having an alkynyl group or a nitrile group undergoes a [2+2+2] cycloaddition reaction in the presence of a catalyst.

[0065] The [2+2+2] cycloaddition mentioned here means, for example, that, taking a carbon-carbon triple bond as an example, three triple bonds are cyclized to form a six-membered ring to form a benzene skeleton as described below. In the following formula, R is an organic group.

[0066] [Chemical formula 1]

[0067]

[0068] In addition, in the above formula, when the carbon-carbon triple bond is replaced by a carbon-nitrogen triple bond (cyano group), a corresponding heterocyclic skeleton such as a pyridine ring is formed.

[0069] The components contained in the curable silicone composition of the present invention are described below.

[0070] (A)Ingredients

[0071] The component (A) is an organopolysiloxane having at least one acetylenic group or nitrile group in one molecule.

[0072] The alkynyl group is preferably a monovalent hydrocarbon group having 2 to 8 carbon atoms with a carbon-carbon triple bond, and more preferably a monovalent hydrocarbon group having 2 to 6 carbon atoms with a carbon-carbon triple bond. Examples include: terminal alkynes such as ethynyl and propargyl; internal alkynes having a group other than a hydrogen atom on the carbon atom forming the carbon-carbon triple bond. It is preferably a terminal alkyne, and particularly preferably an ethynyl group. The nitrile group is preferably a monovalent functional group having 1 to 8 carbon atoms with a carbon-nitrogen triple bond, and more preferably a monovalent functional group having 1 to 6 carbon atoms with a carbon-nitrogen triple bond. Examples include: cyano, cyanomethyl, cyanoethyl, etc., and preferably a cyano group.

[0073] The alkynyl group or nitrile group may be bonded to either the silicon atom at the molecular chain terminal or the silicon atom in the molecular chain, or may be bonded to both.

[0074] The organic groups other than the alkynyl group or the nitrile group bonded to the silicon atom of the organopolysiloxane are: unsubstituted or substituted monovalent hydrocarbon groups having 1 to 18 carbon atoms, preferably unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and more preferably unsubstituted or substituted monovalent hydrocarbon groups having 1 to 8 carbon atoms. For example, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, and decyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl, phenethyl, and phenylpropyl; or groups formed by replacing some or all of the hydrogen atoms of the above groups with halogen atoms such as fluorine, bromine, and chlorine, such as chloromethyl, chloropropyl, bromoethyl, and trifluoropropyl. Methyl and trifluoropropyl are particularly preferred.

[0075] The kinematic viscosity of the organopolysiloxane at 25° C. is 1 to 20,000,000 mm 2 / s, preferably 10~1,000,000mm 2 / s, more preferably 60~30,000mm 2 / s. If the kinematic viscosity is 1mm 2 / s or more, the physical properties of the curable silicone composition are good. If it is 20,000,000 mm 2 / s or less, the spreadability of the curable silicone composition is sufficient.

[0076] In the present invention, the kinematic viscosity is a value measured at 25° C. using an Ubbelohde-type Ostwald viscometer (the same shall apply hereinafter).

[0077] As long as the organopolysiloxane has the above-mentioned properties, its molecular structure is not particularly limited, and examples thereof include a linear structure, a branched structure, a partially branched structure, or a linear structure having a cyclic structure. Particularly preferred is a linear structure in which the main chain is composed of repeated diorganosiloxane units and both ends of the molecular chain are capped with triorganosiloxy groups. The organopolysiloxane having the linear structure may have a branched structure or a cyclic structure in part.

[0078] The organopolysiloxane may be used alone or in combination of two or more.

[0079] (B) Ingredients

[0080] The component (B) is a transition metal compound, a typical metal compound, or a combination thereof that can catalyze a [2+2+2] cycloaddition reaction (e.g., Non-Patent Document 1), and is added as a catalyst for curing the curable silicone composition of the present invention. Here, "capable of catalyzing a [2+2+2] cycloaddition reaction" means having catalytic activity for a [2+2+2] cycloaddition reaction.

[0081] Examples of the transition metal compound having catalytic activity for the [2+2+2] cycloaddition reaction include the following compounds.

[0082] Transition metal compounds can be composed of a central metal atom, a ligand, and a counter ion. As the central metal atom, atoms of Groups 4 to 12 can be listed. Specifically, Groups 4 (titanium (Ti), zirconium (Zr), hafnium (Hf)), Groups 5 (vanadium (V), niobium (Nb), tantalum (Ta)), Groups 6 (chromium (Cr), molybdenum (Mo), tungsten (W)), Groups 7 (manganese (Mn), rhenium (Re)), Groups 8 (iron (Fe), ruthenium (Ru), osmium (Os)), Groups 9 (cobalt (Co), rhodium (Rh), iridium (Ir)), Groups 10 (nickel (Ni), palladium (Pd), platinum (Pt)), Groups 11 (copper (Cu)), and Groups 12 (zinc (Zn)). The central metal atom can be one or more than two kinds. When there are more than two kinds, they can all be the same metal or a combination of different metals.

[0083] The ligand is not particularly limited, and examples thereof include: carbonyl (CO); ammonia; water; F - , Cl - Br - ,I - Halide ions; cyanide ions (CN -); phosphine (PR3) such as triphenylphosphine; olefins such as cyclopentadienyl (Cp) group, pentamethylcyclopentadienyl (Cp*) group, cyclooctadienyl (COD) group, cyclooctatrienyl (COT) group, norbornene group, norbornadienyl group; α,β-unsaturated ketones such as dibenzylideneacetone; acyl groups such as acetyl group and benzoyl group; β-diketones such as acetylacetone (acac); β-ketoesters such as ethyl acetoacetate; amines such as alkylamines, alkylenediamines, aniline, pyridine, etc.; or alkoxy groups. Among them, carbonyl (CO), cyclopentadienyl (Cp) group, triphenylphosphine, and dibenzylideneacetone are preferred.

[0084] The ligand may be a monodentate ligand or a bidentate or higher polydentate ligand.

[0085] The counter ion is not particularly limited, and examples thereof include halide ions, cyanide ions, carbonate ions, and PF6 ions that can also serve as ligands. - 、BF4 - 、NO3 - ,BPh4 - 、ClO4 - anions such as ammonium, sulfonium, and phosphonium cations. Among them, halide ions are preferred, and Cl - .

[0086] When MQ n When representing a transition metal compound, M is Ti, Nb, Ta, Fe, Ru, Co, Rh, Ir, Ni or Pd, preferably Ti, Nb, Ta, Co, Rh or Pd, more preferably Co, Rh or Pd. Q is a cyclopentadienyl group, a halogen atom, an OAc group (Ac represents an acetyl group), an acetylacetonato group or an alkoxy group. Examples of the halogen atom include I, Br, Cl and F, preferably I, Br and Cl. n is a number corresponding to the valence of M. MQ n Two or more different types of Q may be contained.

[0087] The transition metal complex preferably comprises MQ n The complex of the transition metal salt or its hydrate represented by MQ n -L m The complex represented. About MQ n , as described above. The ligand L is 2-(2,6-diisopropylphenyl)iminomethylpyridine (dipimp), triphenylphosphine (PPh3), 1,2-bis(diphenylphosphine)ethane (dppe), 2,6-bis(2,6-diisopropylphenyliminomethyl)pyridine or cyclooctadienyl (cod), etc. m is an integer. The transition metal complex can be a mononuclear complex or a binuclear complex.

[0088] More specifically, transition metal salts include Ti(Oi-Pr)4, CpTi(Oi-Pr)3, CpTiCl3, NbCl5, TaCl5, FeCl2, FeCl3, FeBr2, FeBr3, FeI2, FeI3, Fe(OAc)2, Fe(OAc)3, Fe(acac)2, Fe(acac)3, CoCl2, CoCl3, CoBr2, CoBr3, CoI2, CoI3, Co(OAc)2, Co(OAc)3, Co(acac)2, Co(acac)3, RhCl3, RuCl3, IrCl3, etc. i-Pr represents an isopropyl group, and acac represents an acetylacetonate group.

[0089] It is also possible to use a catalyst obtained by reacting a transition metal salt selected from the above-mentioned transition metal salts or their hydrates, or a complex of these transition metal salts or their hydrates (for example, a complex with the above-mentioned ligand L) with a reducing agent (for example, a reducing agent such as a metal, organic metal, metal hydride or alkylamine described later).

[0090] As the transition metal salt, CoQ is also preferred. a 2(Q a A salt represented by (representing a cyclopentadienyl group, a halogen atom, an OAc group or an acetylacetonato group). A catalyst can also be used which is formed by making CoQ a 2 or a transition metal salt or a hydrate thereof, or CoQ a 2 or a hydrate thereof (for example, a complex with the above-mentioned ligand L) and a reducing agent (for example, a reducing agent such as a metal, an organic metal, a metal hydride or an alkylamine described later).

[0091] Examples of reducing agents include metals (e.g., Zn, Mn, Al, Mg, etc.), organic metals (e.g., Grignard reagents, organic lithium, etc.), metal hydrides (e.g., NaBH4, LiAlH4, etc.), alkylamines (e.g., trialkylamines such as triethylamine, etc.), etc. Metals such as Zn, Mn, Al, and Mg are preferably in the form of powders.

[0092] Examples of such transition metal complexes include [Mo(CO)3Cp]2, [W(CO)3Cp]2, Co2(CO)8, NbCl5, TaCl5, dicarbonylcyclopentadienylcobalt(I) (CpCo(CO)2), tetrakis(triphenylphosphine)palladium(0), tris(dibenzylideneacetone)dipalladium(0), tris(triphenylphosphine)rhodium(I) chloride, and Pd(Ph3P)2Cl2-CuI. If CpCo(CO)2 is used, it can be activated by UV irradiation.

[0093] The transition metal complex can be dissolved or dispersed in a solvent as needed before dilution. As such a solvent, any known solvent can be used, for example: alcohols such as methanol; ketones such as acetone; hydrocarbon solvents such as hexane, toluene, and xylene; halogenated hydrocarbon solvents such as dichloromethane, chloroform, and 1,2-dichloroethane; esters such as ethyl acetate; and solvents having trimethylsilyl groups at both ends and a kinematic viscosity of 50,000 mm at 25°C. 2 / s dimethyl polysiloxane and other polysiloxanes.

[0094] Typical metal compounds having catalytic activity for the [2+2+2] cycloaddition reaction include the following compounds.

[0095] Typical metal compounds can be composed of a central metal atom, a ligand, and a counter ion. As the central metal atom, atoms of Groups 13 and 14 can be listed. Specifically, Groups 13 (aluminum (Al), gallium (Ga), indium (In), thallium (Tl)), and Groups 14 (tin (Sn), lead (Pb)) can be listed. Specifically, organic metal compounds of the above metals such as organic aluminum such as triethyl aluminum and organic tin such as Ph4Sn can be listed.

[0096] The typical metal compound can also be used after being dissolved or dispersed in a solvent as needed, similarly to the transition metal complex. As such a solvent, the solvents listed for the transition metal complex can be used.

[0097] The concentration of the transition metal complex and the typical metal compound in the solvent (catalyst concentration) can be set as needed, and can be, for example, 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the mass of the central metal. The desired composition can be prepared by adding the diluent in a manner that becomes the blending amount of the (B) component described later.

[0098] The (B) component can use the previously known catalysts used in the [2+2+2] cycloaddition reaction (disclosed in, for example, Patent Documents 5, 6 and Non-Patent Document 1). Specifically, it can include: transition metal compounds such as cobalt, palladium, rhodium, ruthenium, iron, titanium, zirconium / nickel, zirconium / copper, and tantalum; typical metal compounds such as silicon and germanium, preferably transition metal compounds that can catalyze the [2+2+2] cycloaddition reaction, more preferably transition metal complexes, among which relatively easy-to-obtain cobalt, palladium, rhodium, and ruthenium catalysts (transition metal complexes) are preferred. In addition, the (B) component can be used alone or in combination of two or more, and can be any combination of transition metal compounds and typical metal compounds. As examples, NbCl5-Ph4Sn and TaCl5-Ph4Sn can be listed. Here, "system" means "containing", for example, "cobalt system" means containing cobalt, and "transition metal compound" means a compound containing a transition metal.

[0099] The catalyst active for the [2+2+2] cycloaddition reaction, i.e., component (B), is particularly preferably dicarbonylcyclopentadienylcobalt (I), tetrakis(triphenylphosphine)palladium (0), tris(dibenzylideneacetone)dipalladium (0), or tris(triphenylphosphine)rhodium (I) chloride.

[0100] The transition metal compound can be obtained by reacting a transition metal salt or a hydrate thereof, or a complex of a transition metal salt or a hydrate thereof with a reducing agent. By reducing the transition metal in this way, a catalytically active species can be generated.

[0101] As reactions of alkynyl groups, for example, the synthesis of substituted polyacetylene using a catalyst as described in Patent Document 4, and the formation of a benzene skeleton by cyclotrimerization of alkynyl groups are known. In relation to the latter, the cycloaddition trimerization reaction of alkynes ([2+2+2] cycloaddition reaction) is used as a polymerization reaction for a bond generation reaction, and is expected to be a useful polymer synthesis method that produces branched polymers (hyperbranched polymers) (Patent Documents 5, 6). In addition, it is also known that a heterocyclic ring such as a pyridine ring is formed by a [2+2+2] cycloaddition reaction of an alkynyl group with a carbon-nitrogen triple bond (cyano group) or an isocyanate group using a catalyst (Non-Patent Document 1). Although it is known that the [2+2+2] cycloaddition reaction is applied to specific ring formation and branched polymer synthesis, no research has been conducted so far on its application to curing reactions.

[0102] The present invention combines an organopolysiloxane having at least one acetylenic group or nitrile group in one molecule with a catalyst active for a [2+2+2] cycloaddition reaction. This is based on the following fact first discovered by the inventors of the present application: the organosilicon composition can be cured by a reaction mechanism that is completely different from the previous curing reaction (addition curing based on hydrosilylation), such as a [2+2+2] cycloaddition. The present invention has the following excellent characteristics that the previous curing forms do not have: since a curing reaction based on a [2+2+2] cycloaddition is adopted, the curing reaction will proceed even if there are substances that inhibit the curing of the addition-curing organosilicon composition, and no reaction control agent is required, and no special temperature management is required during storage and transportation.

[0103] The organopolysiloxane having an alkynyl group or a nitrile group undergoes a [2+2+2] cycloaddition reaction through a catalyst while undergoing the curing reaction in the present invention. As described above, through the [2+2+2] cycloaddition, for example, a carbon-carbon triple bond can be trimerized to form a benzene skeleton, or a carbon-carbon triple bond can be cyclized with a carbon-nitrogen triple bond (CN group) to form a heterocyclic ring such as a pyridine ring, but the above-mentioned cyclic skeleton formed in the curing reaction is a planar and chemically stable structure. Therefore, it is believed that the cured product obtained in the present invention has excellent electrical properties, cold resistance, heat resistance and chemical stability.

[0104] The amount of component (B) added is sufficient as long as it is an effective amount as a catalyst, that is, an effective amount required to promote the curing reaction and cure the curable silicone composition of the present invention. The amount is preferably 0.1 to 10,000 ppm, more preferably 1 to 5,000 ppm, and even more preferably 10 to 3,000 ppm relative to the total composition, based on the mass of the central metal atom. If the amount of the catalyst is above the lower limit, the effect as a catalyst can be obtained, and if it is below the upper limit, the catalytic effect is sufficient and the economic efficiency is good.

[0105] (C) Ingredients

[0106] The curable silicone composition of the present invention may further include an inorganic filler or an organic filler as the component (C). The component (C) is used to impart various properties such as thermal conductivity, heat resistance, reinforcement, electrical conductivity, and designability to the curable silicone composition of the present invention, and is preferably a filler composed of at least one material selected from the group consisting of metals, metal oxides, metal hydroxides, metal nitrides, metal carbides, carbon allotropes, resins, dyes, and pigments, and examples thereof include: metals such as aluminum, silver, copper, and metallic silicon; metal oxides such as aluminum oxide, zinc oxide, magnesium oxide, silicon dioxide, cerium oxide, and iron oxide; metal hydroxides such as aluminum hydroxide and cerium hydroxide; metal nitrides such as aluminum nitride and boron nitride; silicon carbide, etc. Metal carbides; allotropes of carbon such as diamond, graphite, carbon nanotubes, and graphene; resins such as silicone resin powders; dyes such as indigo; pigments such as red iron oxide, etc. In order to impart thermal conductivity to the composition, aluminum, silver, aluminum oxide, zinc oxide, and aluminum nitride are preferably used; in order to impart heat resistance, cerium oxide, cerium hydroxide, and iron oxide are preferably used; in order to impart reinforcement, silicon dioxide such as hydrophobic fumed silica is preferably used; in order to impart conductivity, allotropes of silver, copper, and carbon are preferably used; in order to impart smoothness, silicone resin powder is preferably used; in order to impart designability, dyes and pigments such as indigo and red iron oxide are preferably used.

[0107] If the average particle size of the filler is less than 500 μm, the resulting composition is more uniform, so it is preferably within the range of 500 μm or less, more preferably within the range of 100 μm or less, and further preferably within the range of 40 μm or less. In addition, it is preferably more than 0.01 μm, and particularly preferably more than 0.1 μm. In addition, the average particle size can be obtained in the form of, for example, the volume average value (or median particle size) in the particle size distribution measurement performed by the laser diffraction method. In addition, the shape of the filler is spherical, amorphous, needle-shaped, plate-shaped, etc., and is not particularly limited.

[0108] If the amount of component (C) is 5,000 parts by mass or less relative to 100 parts by mass of component (A), the viscosity will not be too high and the composition will be easy to handle, so it is preferably 5,000 parts by mass or less, preferably 2,000 parts by mass or less. When blended, it is preferably 0.1 parts by mass or more, and particularly preferably 1 part by mass or more.

[0109] Other Ingredients

[0110] The curable silicone composition of the present invention may contain non-reactive organo(poly)siloxanes such as methylpolysiloxane in order to adjust the strength and viscosity of the composition. Hydrolyzable organopolysiloxanes and various modified silicones and hydrolyzable organosilanes may be blended for the purpose of improving the filling property of the filler and imparting adhesion to the composition. In addition, a solvent for adjusting the viscosity of the composition may be blended. In addition, in order to prevent the deterioration of the curable silicone composition, a conventionally known antioxidant such as 2,6-di(tert-butyl)-4-methylphenol may be contained as required. In addition, a flame retardant, a sedimentation inhibitor or a thixotropy enhancer may be blended as required.

[0111] Method for making curable silicone composition

[0112] The method for preparing the curable silicone composition of the present invention is described below. The method for preparing the curable silicone composition of the present invention is not particularly limited, and is characterized in that 100 parts by mass of (A) an organopolysiloxane having at least one acetylenic group or nitrile group in one molecule, and an effective amount of (B) a transition metal compound, a typical metal compound, or a combination thereof that can catalyze a [2+2+2] cycloaddition reaction are mixed. In other words, there is a step of preparing the curable silicone composition by mixing the above-mentioned (A) and (B) components, and the (C) component and other components as needed.

[0113] The following method can be cited: using a mixer such as AWATORI Rentaro (a registered trademark of THINKY CORPORATION), Trimix, twin-mix, Planetary Mixer (all registered trademarks of mixers manufactured by INOUE MFG., INC.), UltraMixer (a registered trademark of mixers manufactured by MIZUHO INDUSTRIAL CO., LTD.), HIVIS DISPER MIX (a registered trademark of mixers manufactured by TokushuKika Kogyo Co., Ltd.), or a method of mixing by manual mixing using a spatula, the above-mentioned (A) and (B) components, and the optional (C) component and other components are usually mixed at 25° C. for 3 minutes to 24 hours, preferably for 5 minutes to 12 hours, and particularly preferably for 10 minutes to 6 hours. In addition, deaeration may be performed during mixing.

[0114] The absolute viscosity of the curable silicone composition of the present invention measured at 25°C is preferably 0.1 to 1,000 Pa·s, more preferably 1 to 700 Pa·s, and further preferably 5 to 500 Pa·s. If the viscosity is 0.1 Pa·s or more, the shape is well maintained and the processability is good. In addition, if the viscosity is 1,000 Pa·s or less, it is easy to spray and apply, and the processability is good. The viscosity can be obtained by adjusting the ratio of the above-mentioned components. In the present invention, the absolute viscosity is the value at 25°C measured using a MALCOM viscometer (rotor A is 10 rpm, shear rate is 6 [1 / s]).

[0115] The curable silicone composition of the present invention can be suitably used for a wide range of applications in the same manner as conventional general curable silicone compositions, and is particularly effective for the following purposes: requiring no special temperature management during storage and transportation; and for use in locations where substances that would inhibit the curing of conventionally known addition-curable silicone compositions exist.

[0116] [Cured silicone]

[0117] The cured organosilicon material of the present invention is obtained by curing the above-mentioned curable organosilicon composition.

[0118] The method for preparing the organosilicon cured product is characterized in that it comprises: a step of mixing 100 parts by mass of (A) an organopolysiloxane having at least one acetylenic group or nitrile group in one molecule and an effective amount of (B) a transition metal compound capable of catalyzing a [2+2+2] cycloaddition reaction; and a step of curing the obtained mixture.

[0119] In addition, the curing method of the above-mentioned curable silicone composition is characterized in that a mixture is cured, wherein the mixture contains (A) an organic polysiloxane having at least one acetylenic group or nitrile group in one molecule; and an effective amount of (B) a transition metal compound, a typical metal compound or a combination thereof that can catalyze a [2+2+2] cycloaddition reaction.

[0120] The curing conditions for curing the curable silicone composition of the present invention are not particularly limited, but the temperature is usually 25 to 200°C, preferably 60 to 180°C, and particularly preferably 80 to 170°C, and the time is usually 3 minutes to 24 hours, preferably 5 minutes to 12 hours, and particularly preferably 10 minutes to 6 hours. The properties of the curable silicone composition after curing are not particularly limited, and examples thereof include gel, low hardness rubber, high hardness rubber, etc.

[0121] [[2+2+2] Cycloaddition reaction product]

[0122] The present invention provides a [2+2+2] cycloaddition reaction product, which is a [2+2+2] cycloaddition reaction product of an organopolysiloxane having at least one alkynyl group or nitrile group in one molecule.

[0123] The method for preparing the above-mentioned [2+2+2] cycloaddition reaction product is characterized in that (B) a transition metal compound, a typical metal compound or a combination thereof capable of catalyzing the [2+2+2] cycloaddition reaction is used to cause (A) an organic polysiloxane having at least one alkynyl group or nitrile group in one molecule to undergo a [2+2+2] cycloaddition reaction, thereby obtaining a product.

[0124] The structure of the [2+2+2] cycloaddition reaction product (organic silicone cured product) can be confirmed by known measuring means such as nuclear magnetic resonance spectroscopy, infrared spectroscopy, and gel permeation chromatography.

[0125] Example

[0126] The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[0127] In the following, the kinematic viscosity at 25°C is the value measured as described above, the catalyst concentration is the concentration based on mass converted to the central metal atom relative to the entire composition, and the average particle size is the average value based on volume in the particle size distribution measurement by laser diffraction. In addition, the structure of the obtained silicone cured product was confirmed by nuclear magnetic resonance spectroscopy, infrared spectroscopy, and gel permeation chromatography.

[0128] First, in order to prepare the curable silicone composition of the present invention, the following components are prepared.

[0129] (A)Ingredients

[0130] A-1: Both ends are capped with acetylene groups and the kinematic viscosity at 25°C is 600 mm 2 / s dimethyl polysiloxane

[0131] A-2: Both ends are capped with acetylene groups and the kinematic viscosity at 25°C is 900 mm 2 / s dimethyl polysiloxane

[0132] A-3: M E 5T 10 (The kinematic viscosity at 25°C is 15 mm 2 / s)

[0133] (M E HC≡CMe2SiO 1 / 2 , T is MeSiO 3 / 2 )

[0134] A-4: The kinematic viscosity at 25°C represented by the following formula (1) is 500 mm 2 / s organic polysiloxane

[0135] [Chemical formula 2]

[0136]

[0137] A-5 (for comparison): Both ends are vinyl-terminated and the kinematic viscosity at 25°C is 600 mm 2 / s dimethyl polysiloxane

[0138] (B) Ingredients

[0139] B-1: Cyclopentadienylcobalt(I) dicarbonyl

[0140] B-2: A solution prepared by dissolving tetrakis(triphenylphosphine)palladium(0) in dichloromethane (catalyst concentration: 1% by mass)

[0141] B-3: A solution prepared by dissolving tris(dibenzylideneacetone)dipalladium(0) in dichloromethane (catalyst concentration: 1% by mass)

[0142] B-4: A solution prepared by dissolving tris(triphenylphosphine)rhodium chloride (I) in dichloromethane (catalyst concentration: 1% by mass)

[0143] B-5: Dissolve tris(dibenzylideneacetone)dipalladium(0) in a solution having trimethylsilyl groups at both ends and a kinematic viscosity of 50,000 mm at 25°C. 2 / s dimethylpolysiloxane solution (catalyst concentration: 5% by mass)

[0144] B-6 (for comparison): a solution prepared by dissolving a platinum-divinyltetramethyldisiloxane complex in the same dimethylpolysiloxane as A-5 (platinum atom content: 1% by mass)

[0145] (C) Ingredients

[0146] C-1: Aluminum powder with an average particle size of 8 μm

[0147] C-2: Zinc oxide powder with an average particle size of 0.4 μm

[0148] Other Ingredients

[0149] D-1: Hydrolyzable organosilane represented by the following formula (2)

[0150] [Chemical formula 3]

[0151]

[0152] D-2 (for comparison): 1-ethynyl-1-cyclohexanol represented by the following formula (3)

[0153] [Chemical formula 4]

[0154]

[0155] D-3 (for comparison): methyl hydrogen dimethyl polysiloxane represented by the following formula (4)

[0156] (Kinematic viscosity at 25°C = 100 mm 2 / s)

[0157] [Chemical formula 5]

[0158]

[0159] D-4 (for comparison): methyl hydrogen dimethyl polysiloxane represented by the following formula (5)

[0160] (Kinematic viscosity at 25°C = 28 mm 2 / s)

[0161] [Chemical formula 6]

[0162]

[0163] D-5 (for comparison): methyl hydrogen dimethyl polysiloxane represented by the following formula (6)

[0164] (Kinematic viscosity at 25°C = 17 mm 2 / s)

[0165] [Chemical formula 7]

[0166]

[0167] [Examples 1 to 4]

[0168] Preparation of curable silicone composition[1]

[0169] The above-mentioned (A) and (B) components were mixed in the amounts shown in Table 1 below by manual mixing using a spatula to prepare a curable silicone composition. The properties of each of the obtained curable silicone compositions after heat curing at 150° C. for 1.5 hours were confirmed. The results are shown in Table 1.

[0170] [Table 1]

[0171]

[0172] From the results in Table 1, it can be seen that the curable silicone compositions of Examples 1 to 4 that meet the requirements of the present invention can be cured into a gel-rubber state by heating. In addition, it was confirmed by nuclear magnetic resonance spectroscopy, infrared spectroscopy, and gel permeation chromatography that the obtained silicone cured product is a [2+2+2] cycloaddition reaction product.

[0173] [Examples 5 to 8, Comparative Examples 1 to 3]

[0174] Preparation of curable silicone composition[2]

[0175] The above-mentioned (A), (B), (C), and (D) components were mixed using AWATORI Rentaro (manufactured by THINKY CORPORATION) in the amounts shown in Tables 2 and 3 below, thereby preparing a curable silicone composition. For each of the obtained curable silicone compositions, the time until curing at 25° C. was measured. In addition, a certain amount of a substance that inhibits curing of a conventionally known addition-curable silicone composition, namely, 2-phenylimidazole represented by the following formula (7), was added, and the properties of the composition after heat curing at 150° C. for 1.5 hours were confirmed. The results are shown in Tables 2 and 3.

[0176] [Chemical formula 8]

[0177]

[0178] [Table 2]

[0179]

[0180] [Table 3]

[0181]

[0182] From the results in Tables 2 and 3, it can be seen that the silicone compositions of Examples 5 to 8 that meet the requirements of the present invention have a very long time until they cure at 25°C, and even if 10 to 100 ppm of 2-phenylimidazole, a substance that inhibits the curing of conventional addition-curing silicone compositions, is added, they can still be cured into a rubber state by heating. In addition, it was confirmed by nuclear magnetic resonance spectroscopy, infrared spectroscopy, and gel permeation chromatography that the obtained silicone cured product is a [2+2+2] cycloaddition reaction product.

[0183] On the other hand, Comparative Examples 1 to 3 are conventionally known addition-curing silicone compositions. Although Comparative Example 1 can be cured into a rubbery state by heating even when 100 ppm of 2-phenylimidazole is added, the time until curing at 25°C is extremely short at 30 hours. Although the time until curing at 25°C is extended to 7 days for Comparative Examples 2 and 3, it is very short compared to Examples 5 to 8. In addition, when 1.0 ppm of 2-phenylimidazole is added, the properties of the composition after heat curing become gel-like, and when 10 ppm is added, it is not cured, so it is judged that the curability has also been reduced.

[0184] From the results in Tables 1 to 3, it can be seen that the curable silicone composition of the present invention (Examples 1 to 8) takes a sufficiently long time to cure at room temperature (25°C), and can be sufficiently cured by heating even in the presence of substances that inhibit the curing of conventional addition-curable silicone compositions. This is based on the feature of the present invention that the curable silicone composition is cured by a [2+2+2] cycloaddition reaction (in other words, the obtained silicone cured product is a [2+2+2] cycloaddition reaction product).

[0185] Therefore, the curable silicone composition of the present invention has the following advantages: it can be stored and transported at room temperature, and is not easily affected by substances that inhibit the curing of conventionally known addition-curable silicone compositions. As a result, no special temperature management is required during storage and transportation, and the environmental burden can be reduced. It can also be used in places where substances that inhibit the curing of conventionally known addition-curable silicone compositions exist.

[0186] In addition, the [2+2+2] cycloaddition reaction product of the present invention has the following advantages and is excellent as the main component of a curable silicone composition: it can be easily and efficiently obtained by a catalytic cycloaddition reaction of an organic polysiloxane having at least one acetylenic group or nitrile group in one molecule, and does not require a reaction control agent. Even if a substance that would inhibit curing in a general hydrosilylation reaction coexists, it is not easily affected by it.

[0187] This specification contains the following protocols.

[0188] [1]: A curable silicone composition, characterized in that it comprises:

[0189] 100 parts by mass of (A) an organopolysiloxane having at least one acetylenic group or nitrile group in one molecule; and

[0190] An effective amount of (B) a transition metal compound, a typical metal compound or a combination thereof capable of catalyzing a [2+2+2] cycloaddition reaction.

[0191] [2]: The curable silicone composition according to [1], wherein the component (A) has a kinematic viscosity of 1 to 20,000,000 mm at 25°C. 2 / s of organopolysiloxane.

[0192] [3]: The curable silicone composition according to [1] or [2], wherein the component (A) is an organopolysiloxane having at least one acetylenic group in one molecule.

[0193] [4]: The curable silicone composition according to any one of [1] to [3], wherein the component (A) is an organopolysiloxane having at least one ethynyl group in one molecule.

[0194] [5]: The curable silicone composition according to any one of [1] to [4], wherein the component (B) is a transition metal complex capable of catalyzing a [2+2+2] cycloaddition reaction.

[0195] [6]: The curable silicone composition according to any one of [1] to [5], further comprising (C) at least one inorganic filler or organic filler, wherein the amount of the component (C) is 0.1 to 5,000 parts by mass relative to 100 parts by mass of the component (A).

[0196] [7]: The curable silicone composition according to [6], characterized in that the component (C) is a filler composed of one or more materials selected from the group consisting of metals, metal oxides, metal hydroxides, metal nitrides, metal carbides, carbon allotropes, resins, dyes, and pigments.

[0197] [8]: A cured organosilicon product obtained by curing the curable organosilicon composition according to any one of [1] to [7].

[0198] [9]: A method for preparing a curable silicone composition, characterized by mixing 100 parts by mass of (A) an organopolysiloxane having at least one acetylenic group or nitrile group in one molecule and an effective amount of (B) a transition metal compound, a typical metal compound or a combination thereof capable of catalyzing a [2+2+2] cycloaddition reaction.

[0199]

[10] : A method for preparing a cured organosilicon material, characterized in that it comprises: a step of mixing 100 parts by mass of (A) an organopolysiloxane having at least one acetylenic group or nitrile group in one molecule and an effective amount of (B) a transition metal compound, a typical metal compound or a combination thereof capable of catalyzing a [2+2+2] cycloaddition reaction; and a step of curing the resulting mixture.

[0200]

[11] : A method for curing a curable silicone composition, characterized in that a mixture is cured, wherein the mixture comprises:

[0201] (A) an organopolysiloxane having at least one acetylenic group or nitrile group in one molecule; and

[0202] An effective amount of (B) a transition metal compound, a typical metal compound or a combination thereof capable of catalyzing a [2+2+2] cycloaddition reaction.

[0203]

[12] : A [2+2+2] cycloaddition reaction product, which is a [2+2+2] cycloaddition reaction product of an organopolysiloxane having at least one alkynyl group or nitrile group in one molecule.

[0204]

[13] : A method for preparing a [2+2+2] cycloaddition reaction product, characterized in that (B) a transition metal compound, a typical metal compound or a combination thereof capable of catalyzing a [2+2+2] cycloaddition reaction is used to cause (A) an organopolysiloxane having at least one alkynyl group or nitrile group in one molecule to undergo a [2+2+2] cycloaddition reaction, thereby obtaining a product.

[0205] In addition, the present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are examples, and any technical solution having substantially the same structure and exerting the same technical effect as the technical concept described in the claims of the present invention is included in the technical scope of the present invention.

Claims

1. A curable silicone composition, characterized in that: It contains: 100 parts by mass of (A) an organopolysiloxane having one or more acetylenic groups or nitrile groups in one molecule; and An effective amount of (B) a transition metal compound, a typical metal compound or a combination thereof capable of catalyzing a [2+2+2] cycloaddition reaction.

2. The curable silicone composition according to claim 1, characterized in that: The component (A) has a kinematic viscosity of 1 to 20,000,000 mm at 25°C. 2 / s of organopolysiloxane.

3. The curable silicone composition according to claim 2, characterized in that: The component (A) is an organopolysiloxane having one or more acetylenic groups in one molecule.

4. The curable silicone composition according to claim 3, characterized in that: The component (A) is an organopolysiloxane having one or more ethynyl groups in one molecule.

5. The curable silicone composition according to claim 1, characterized in that: The component (B) is a transition metal complex capable of catalyzing a [2+2+2] cycloaddition reaction.

6. The curable silicone composition according to any one of claims 1 to 5, characterized in that: It further contains (C) one or more inorganic fillers or organic fillers, wherein the amount of the component (C) is 0.1 to 5,000 parts by mass based on 100 parts by mass of the component (A).

7. The curable silicone composition according to claim 6, characterized in that: The component (C) is a filler composed of one or more materials selected from the group consisting of metals, metal oxides, metal hydroxides, metal nitrides, metal carbides, carbon allotropes, resins, dyes, and pigments. 8 . A cured organosilicon product, which is obtained by curing the curable organosilicon composition according to claim 1 .

9. A cured organosilicon product obtained by curing the curable organosilicon composition according to claim 6 or 7.

10. A method for preparing a curable silicone composition, characterized in that: 100 parts by mass of (A) an organopolysiloxane having one or more alkynyl groups or nitrile groups in one molecule and an effective amount of (B) a transition metal compound, a typical metal compound or a combination thereof capable of catalyzing a [2+2+2] cycloaddition reaction are mixed.

11. A method for preparing a cured organosilicon material, characterized in that: The method comprises: mixing 100 parts by mass of (A) an organopolysiloxane having one or more alkynyl groups or nitrile groups in one molecule and an effective amount of (B) a transition metal compound, a typical metal compound or a combination thereof capable of catalyzing a [2+2+2] cycloaddition reaction; and curing the obtained mixture.

12. A method for curing a curable silicone composition, characterized in that: allowing a mixture to solidify, the mixture comprising: (A) an organopolysiloxane having one or more acetylenic groups or nitrile groups in one molecule; and An effective amount of (B) a transition metal compound, a typical metal compound or a combination thereof capable of catalyzing a [2+2+2] cycloaddition reaction.

13. A [2+2+2] cycloaddition reaction product, which is a [2+2+2] cycloaddition reaction product of an organopolysiloxane having one or more alkynyl groups or nitrile groups in one molecule.

14. A method for preparing a [2+2+2] cycloaddition reaction product, characterized in that: The product is obtained by subjecting (A) an organopolysiloxane having one or more alkynyl or nitrile groups in one molecule to a [2+2+2] cycloaddition reaction using (B) a transition metal compound, a typical metal compound or a combination thereof that can catalyze a [2+2+2] cycloaddition reaction.

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