Organosilicon compound and polymer using the same

Abstract

To provide an organosilicon compound in the form of a double-decker silsesquioxane structure having a non-aromatic ring substituent at a cage vertex, a silsesquioxane derivative bearing a functional group derived from the compound, and a polymer composed of the derivatives.SOLUTION: An organosilicon compound is represented by formula (1). In formula (1), R independently denotes hydrogen, halogen, alkyl, cycloalkyl, or the like, and Y denotes a crosslink including Si.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to organosilicon compounds and polymers using the same, more specifically to organosilicon compounds having a silsesquioxane skeleton and polymers using the same. More specifically, the present invention relates to silsesquioxane structures having aliphatic or other substituents, preferably alicyclic substituents, at the vertices of the cage structure, and to silsesquioxane derivatives derived therefrom having functional groups such as amino groups, hydrosilyl groups, glycidyl groups, hydroxyl groups, acetoxy groups, carboxyl groups, methacryloxy groups, chloropropyl groups, vinyl groups, and siloxane groups, as well as polymers comprising these derivatives. In this specification, the term "vertices of the cage structure" refers to the eight Si atoms to which the eight R's are bonded in formula (1) described below. [Background technology]

[0002] Silsesquioxane compounds have been identified as having ladder structures, fully condensed structures, incompletely condensed structures, and amorphous structures, and much research has been conducted on these. Among these, silsesquioxanes with fully condensed and incompletely condensed structures, which are the easiest to control, have attracted attention, and Hybrid Plastics has commercially marketed silsesquioxane derivatives with various functional groups introduced into them (Non-Patent Document 1).

[0003] However, conventional incompletely condensed and fully condensed silsesquioxanes and their derivatives have poor solubility, and when used in coating materials, there are limitations on film-forming properties and the amount that can be added, making it difficult to effectively use them in a wide range of applications. A double-decker structure silsesquioxane (Patent Document 1) that overcomes these drawbacks has been developed, and its application to various materials has been investigated.

[0004] On the other hand, many of the double-decker silsesquioxanes and their derivatives reported to date have phenyl substituents at the apex of the cage structure. While aromatic structures such as phenyl substituents exhibit high heat resistance, their conjugated ring structure is prone to intermolecular interactions and conjugation with adjacent structures, potentially resulting in significant concerns about coloration of polyimide materials, as well as refractive index and dielectric properties, leaving room for improvement. Recently, a study has reported that the apex of the cage structure is substituted with a non-aromatic ring substituent by nuclear hydrogenation of the phenyl group at the apex (Patent Document 2). If the hydrogenation rate is insufficient, aromatic ring structures remain in the material, raising concerns about discoloration during storage and curing. Furthermore, it can be difficult to synthesize double-decker silsesquioxanes and their derivatives that have an alicyclic substituent at the apex of the cage structure and a substituent or functional group with an unsaturated bond in a portion other than the apex of the cage structure through nuclear hydrogenation. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2004 / 024741 (Patent No. 4470738) [Patent Document 2] Japanese Patent Publication No. 2022-146347 [Non-patent literature]

[0006] [Non-Patent Document 1] Ronald H. Bunny, Maki Ito, Akihito Sakakibara, and Toshio Suzuki, "Silsesquioxanes," Chemical Review, American Chemical Society, 1995, Vol. 95, No. 5, pp. 1409-1430 (Chem. Rev. 95, 1409-1430 (1995)) Summary of the Invention [Problem to be solved by the invention]

[0007] In view of the problems of the prior art described above, the present invention aims to provide an organosilicon compound having a double-decker silsesquioxane structure with non-aromatic ring substituents at the vertices of the cage structure, as well as silsesquioxane derivatives derived therefrom having functional groups such as amino groups, hydrosilyl groups, glycidyl groups, hydroxyl groups, acetoxy groups, carboxyl groups, methacryloxy groups, chloropropyl groups, vinyl groups, and siloxane groups, and polymers comprising these derivatives. [Means for solving the problem]

[0008]

[0003] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have succeeded in synthesizing an organosilicon compound having a double-decker silsesquioxane structure with a non-aromatic ring substituent at the apex of the cage structure, which can fully impart the properties expected of silsesquioxanes, by replacing the aromatic ring substituent at the apex of the cage structure with a non-aromatic ring substituent such as an aliphatic substituent. Furthermore, they have succeeded in deriving the terminal functional groups of the structure into functional groups such as amino groups, hydrosilyl groups, glycidyl groups, hydroxyl groups, acetoxy groups, carboxyl groups, methacryloxy groups, chloropropyl groups, vinyl groups, and siloxane groups, and have found that this can produce precursors of polymers useful in the development of useful optical components, dielectric materials, electronic components, and the like, thereby completing the present invention.

[0009] The present invention includes the following configurations. [1] An organosilicon compound represented by formula (1): TIFF2025125602000002.tif4174In formula (1), R independently represents hydrogen, halogen, alkyl having 1 to 45 carbon atoms, or cycloalkyl having 4 to 18 carbon atoms; in the alkyl having 1 to 45 carbon atoms, at least one hydrogen may be replaced by fluorine, and at least one -CH2- may be replaced by -O- or cycloalkylene having 4 to 18 carbon atoms, and in the cycloalkyl having 4 to 18 carbon atoms, at least one hydrogen may be replaced by fluorine or alkyl having 1 to 3 carbon atoms; Y represents a group selected from the groups represented by formula (2-1) or formula (2-2), and two Ys may be the same or different; TIFF2025125602000003.tif1547 TIFF2025125602000004.tif3053 In formula (2-1), R 1 is alkyl having 1 to 45 carbon atoms, aryl having 6 to 45 carbon atoms, or arylalkyl having 7 to 45 carbon atoms; in the alkyl having 1 to 45 carbon atoms, at least one hydrogen may be replaced by fluorine, and at least one -CH2- may be replaced by -O-, -CH=CH-, cycloalkylene having 4 to 18 carbon atoms, or cycloalkenylene having 4 to 18 carbon atoms; in the aromatic ring of the aryl having 6 to 45 carbon atoms and arylalkylene having 7 to 45 carbon atoms, at least one hydrogen may be replaced by fluorine; in the alkylene of the arylalkyl having 7 to 45 carbon atoms, the number of carbon atoms is 1 to 39, and at least one -CH2- may be replaced by -O-, -CH=CH-, or cycloalkylene; and Z is R 1 It is a group, functional group or group having a functional group having the same definition as above. In formula (2-2), Q is —O—, —CH—, or a single bond. 1 is R 1 A group, functional group, or group having a functional group having the same definition as 1 may be the same group or may be composed of different groups. [2] In formula (1) and formula (2-1), R 1is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, or phenyl. [3] The organosilicon compound according to [1] or [2], wherein in formula (1) of claim 1, R is independently alkyl having 1 to 12 carbon atoms or cycloalkyl having 4 to 10 carbon atoms; in the alkyl having 1 to 12 carbon atoms, at least one hydrogen may be replaced by fluorine, and at least one -CH2- may be replaced by -O- or cycloalkylene having 4 to 10 carbon atoms; and in the cycloalkyl having 4 to 10 carbon atoms, at least one hydrogen may be replaced by fluorine or alkyl having 1 to 3 carbon atoms. [4] The organosilicon compound according to any one of [1] to [3], wherein in formula (1) of claim 1, R is independently a cycloalkyl having 4 to 10 carbon atoms; in the cycloalkyl having 4 to 10 carbon atoms, at least one hydrogen may be replaced by fluorine or an alkyl having 1 to 3 carbon atoms; and when the cycloalkyl in which at least one hydrogen is replaced by fluorine or an alkyl having 1 to 3 carbon atoms has multiple substituents, these substituents may be the same or different groups. [5] The organosilicon compound according to any one of [1] to [4], wherein in formula (1) of claim 1, all R are the same group selected from cycloalkyl having 4 to 10 carbon atoms; in the cycloalkyl having 4 to 10 carbon atoms, at least one hydrogen may be replaced by fluorine or alkyl having 1 to 3 carbon atoms, and when the cycloalkyl having at least one hydrogen replaced by fluorine or alkyl having 1 to 3 carbon atoms has multiple substituents, these substituents may be the same group or different groups. [6] The organosilicon compound according to any one of [1] to [5], wherein in formula (1) of claim 1, all R are the same group selected from cycloalkyl having 4 to 10 carbon atoms in which at least one hydrogen may be replaced by fluorine or alkyl having 1 to 3 carbon atoms, and when the cycloalkyl in which at least one hydrogen is replaced by fluorine or alkyl having 1 to 3 carbon atoms has multiple substituents, these substituents may be the same group or different groups. [7] The organosilicon compound according to any one of [1] to [6], wherein in the formula (1) of claim 1, all R are cyclohexyl. [8] In formula (1) and formula (2-1) or formula (2-2), R 1 is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, or phenyl; and Z or Z 1 is a functional group or a group having a functional group, the functional group being a group directly bonded to the Si atom and selected from hydrogen, halogen, -OH, alkoxy, alkenyl and fluorinated alkyl, the group having a functional group being a group composed of a divalent group and a functional group bonded to the Si atom via the divalent group, the divalent group being a divalent group selected from alkylene, alkylcycloalkylene, alkylenephenylene, alkylphenylene and alkylphenylalkylene, in which at least one -CH2- may be replaced by -O- in the alkylene and alkyl in these divalent groups, The organosilicon compound according to any one of [1] to [7], wherein the functional group bonded to the Si atom via is a group selected from hydrogen, halogen, -OH, fluorinated alkyl, alkoxy, carboxyl, 2-oxapropanedioyl, carboxylic anhydride residue, maleimide residue, acetoxy, vinyloxycarbonyl, allyloxycarbonyl, acryloyloxy, methacryloyloxy, polyalkyleneoxy, oxiranyl, 3,4-epoxycyclohexyl, oxetanyl, alkenyl, cycloalkenyl, -NH2, -CN, -NCO, -SH, and -PH2. [9] The organosilicon compound according to [8], wherein in formula (1) of claim 1, R is independently alkyl having 1 to 12 carbon atoms or cycloalkyl having 4 to 10 carbon atoms; in the alkyl having 1 to 12 carbon atoms, at least one hydrogen may be replaced by fluorine, and at least one -CH2- may be replaced by -O- or cycloalkylene having 4 to 10 carbon atoms; and in the cycloalkyl having 4 to 10 carbon atoms, at least one hydrogen may be replaced by fluorine or alkyl having 1 to 3 carbon atoms.

[10] The organosilicon compound according to [8] or [9], wherein in formula (1) according to [1], R is independently a cycloalkyl having 4 to 10 carbon atoms; in the cycloalkyl having 4 to 10 carbon atoms, at least one hydrogen may be replaced by fluorine or an alkyl having 1 to 3 carbon atoms; and when the cycloalkyl in which at least one hydrogen is replaced by fluorine or an alkyl having 1 to 3 carbon atoms has multiple substituents, these substituents may be the same or different groups.

[11] The organosilicon compound according to any one of [8] to

[10] , wherein in formula (1) according to [1], all R are the same group selected from cycloalkyl having 4 to 10 carbon atoms; in the cycloalkyl having 4 to 10 carbon atoms, at least one hydrogen may be replaced by fluorine or alkyl having 1 to 3 carbon atoms, and when the cycloalkyl in which at least one hydrogen is replaced by fluorine or alkyl having 1 to 3 carbon atoms has multiple substituents, these substituents may be the same group or different groups.

[12] The organosilicon compound according to any one of [8] to

[11] , wherein in the formula (1) according to [1], all R are the same group selected from cycloalkyl having 4 to 10 carbon atoms in which at least one hydrogen may be replaced by fluorine or alkyl having 1 to 3 carbon atoms, and when the cycloalkyl in which at least one hydrogen is replaced by fluorine or alkyl having 1 to 3 carbon atoms has multiple substituents, these substituents may be the same group or different groups.

[13] The organosilicon compound according to any one of [8] to

[12] , wherein in the formula (1) according to [1], all R are cyclohexyl.

[14] In formula (1) and formula (2-1) or formula (2-2), Z or Z 1 The organosilicon compound according to any one of [1] to

[13] , wherein is a fluorinated alkyl or a group having a fluorinated alkyl.

[15] In formula (1) and formula (2-1) or formula (2-2), Z or Z 1 is alkenyl, or a group having any one of alkenyl, -OH, carboxyl, 2-oxapropanedioyl, oxiranyl, 3,4-epoxycyclohexyl, oxetanyl, and -NH2.

[16] A polymer obtained by using the organosilicon compound according to

[15] . [Effects of the Invention]

[0010] The organosilicon compound of the present invention is a silsesquioxane structure having a non-aromatic ring substituent at the apex of the cage structure, and its derivatives. In the organosilicon compound of the present invention, the terminal functional group of the silsesquioxane structure having a non-aromatic ring substituent at the apex of the cage structure is converted to a functional group such as an amino group, a hydrosilyl group, a glycidyl group, a hydroxyl group, an acetoxy group, a carboxyl group, a methacryloxy group, a chloropropyl group, a vinyl group, or a siloxane group, thereby obtaining a precursor of the polymer of the present invention, which can be used in the development of useful optical components, dielectric materials, electronic components, etc. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is an IR spectrum of the compound (1) synthesized in Synthesis Example 1. [Figure 2] FIG. 2 is an IR spectrum of the compound (1′) used in the synthesis of the compound (1) in Synthesis Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, the embodiments of the present invention will be described in detail, but the following description is an example (typical example) of the embodiment of the present invention, and the present invention is not limited to these examples. Furthermore, the embodiments of the present invention can be combined as appropriate.

[0013] 1. Organosilicon Compound of the Present Invention In the organosilicon compounds of the present invention, the alkyl having 1 to 45 carbon atoms represented by formula (1) and formula (2-1) may be a straight-chain group or a branched group. In this alkyl having 1 to 45 carbon atoms, when at least one hydrogen is replaced by fluorine or when at least one -CH2- is replaced by -O-, -CH=CH-, cycloalkylene, cycloalkenylene, or the like, the alkyl may be a straight-chain group or a branched group. In the present invention, when it is stated that at least one -CH2- is replaced by -O-, multiple consecutive -CH2- are not replaced by -O- in consideration of the stability of the compound.

[0014] Preferred examples of R in formula (1) include 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-propylcyclohexyl, decahydronaphthyl, tetradecahydroanthracenyl, octadecahydrotetracenyl, hexadecahydropyrenyl, and trifluoromethylcyclohexyl.

[0015] Among these, the more preferred R in formula (1) is a group in which all R are the same, ie, cyclohexyl.

[0016] Y in formula (1) is a group selected from groups represented by formula (2-1) or formula (2-2), and the two Ys may be the same group or different groups. TIFF2025125602000005.tif1547 TIFF2025125602000006.tif3052

[0017] R in formula (2-1) 1Preferred specific examples of include hydrogen, alkoxy having 1 to 44 carbon atoms, alkoxyalkyl having 2 to 44 carbon atoms, alkenyl having 2 to 45 carbon atoms, alkenyloxyalkyl having 3 to 45 carbon atoms, alkyloxyalkenyl having 3 to 45 carbon atoms, alkyl having 1 to 45 carbon atoms in which one -CH2- is replaced by cycloalkylene, alkyl having 1 to 45 carbon atoms in which one -CH2- is replaced by cycloalkenylene, alkyl having 1 to 45 carbon atoms, aryl having 6 to 45 carbon atoms, arylalkyl having 7 to 45 carbon atoms, and groups in which at least one hydrogen in these groups is replaced by fluorine.

[0018] Among these, R in formula (2-1) 1 is more preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl or phenyl.

[0019] In formula (2-1), Z is R 1 R is a group, functional group, or group having a functional group having the same definition as 1 Specifically, groups having the same definition as R are alkyl having 1 to 45 carbon atoms, aryl having 6 to 45 carbon atoms, or arylalkyl having 7 to 45 carbon atoms; in the alkyl having 1 to 45 carbon atoms, at least one hydrogen may be replaced by fluorine, and at least one -CH2- may be replaced by -O-, -CH=CH-, cycloalkylene having 4 to 18 carbon atoms, or cycloalkenylene having 4 to 18 carbon atoms; in the aromatic ring of the aryl having 6 to 45 carbon atoms and arylalkylene having 7 to 45 carbon atoms, at least one hydrogen may be replaced by fluorine; and in the alkylene of the arylalkyl having 7 to 45 carbon atoms, the number of carbon atoms is 1 to 39, and at least one -CH2- may be replaced by -O-, -CH=CH-, or cycloalkylene. 1Among groups having the same definition as above, preferred are groups selected from alkyl having 1 to 45 carbon atoms, alkoxy having 1 to 44 carbon atoms, alkenyl having 2 to 45 carbon atoms, alkyloxyalkenyl having 3 to 45 carbon atoms, phenyl and naphthyl in which at least one hydrogen atom in the aromatic ring may be replaced by fluorine. Preferred specific examples of these groups are R 1 This is the same as that shown for

[0020] Z is a functional group or a group having a functional group, and a preferred specific example is a group in which the functional group is directly bonded to the Si atom and is selected from hydrogen, halogen, -OH, alkoxy, alkenyl, and fluorinated alkyl, and the group having a functional group is a group composed of a divalent group and a functional group bonded to the Si atom via the divalent group, and the divalent group is a divalent group selected from alkylene, alkylcycloalkylene, alkylenephenylene, alkylphenylene, and alkylphenylalkylene, and in the alkylene and alkyl in these divalent groups, at least one -CH2- is replaced with - O-, and the functional group bonded to the Si atom via a divalent group is selected from hydrogen, halogen, -OH, fluorinated alkyl, alkoxy, carboxyl, 2-oxapropanedioyl, carboxylic anhydride residue, maleimide residue, acetoxy, vinyloxycarbonyl, allyloxycarbonyl, acryloyloxy, methacryloyloxy, polyalkyleneoxy, oxiranyl, 3,4-epoxycyclohexyl, oxetanyl, alkenyl, cycloalkenyl, -NH2, -CN, -NCO, -SH, and -PH2.

[0021] Specific examples of halogen include fluorine, chlorine, and bromine. Specific examples of alkenyl include vinyl and allyl. Specific examples of cycloalkenyl include cyclopentadienyl, cyclohexenyl, and norbornenyl.

[0022] In formula (2-1), more preferred specific examples of Z are shown in formulas (3) to (29). TIFF2025125602000007.tif214167

[0023] In formulas (8) to (27), k is 0 or 1, m is an integer of 1 to 4, and n is an integer of 0 to 15. X is a halogen, p is an integer of 1 to 5, q is 2 or 3, and r is an integer of 2 to 200. t is an integer of 1 to 3. E is hydrogen or an alkyl having 1 to 4 carbon atoms, and R is an alkyl having 1 to 6 carbon atoms. In the above examples, -X, -CH2-X, -OH, and -COOH may be bonded to the benzene ring at any position. Specific examples of more preferred halogens include fluorine and chlorine. A more preferred range for r is 2 to 100, and an even more preferred range is 2 to 20.

[0024] In formula (2-2), Q is -O-, -CH2-, or a single bond, and more preferably -O-. 1 is a group having the same definition as Z in formula (2-1), and R 1 A group, functional group, or group having a functional group having the same definition as 1 may be the same group or may be composed of different groups. 1 Specifically, groups having the same definition as above are alkyl having 1 to 45 carbon atoms, aryl having 6 to 45 carbon atoms, or arylalkyl having 7 to 45 carbon atoms; in the alkyl having 1 to 45 carbon atoms, at least one hydrogen may be replaced by fluorine and at least one -CH- may be replaced by -O-, -CH=CH-, cycloalkylene having 4 to 18 carbon atoms, or cycloalkenylene having 4 to 18 carbon atoms; in the aromatic ring of the aryl having 6 to 45 carbon atoms and arylalkylene having 7 to 45 carbon atoms, at least one hydrogen may be replaced by fluorine; and in the alkylene in the arylalkyl having 7 to 45 carbon atoms, the number of carbon atoms is 1 to 39, and at least one -CH- may be replaced by -O-, -CH=CH-, or cycloalkylene.

[0025] The organosilicon compound of the present invention is characterized in that the vertex of the cage structure has a non-aromatic ring substituent such as a cycloalkyl. To synthesize the organosilicon compound of the present invention, it is preferable to use a precursor of the organosilicon compound of the present invention, which is prepared by starting from a cage silsesquioxane silanol having an aromatic ring substituent at the vertex of the cage structure and converting the aromatic ring substituent at the vertex of the cage structure to a non-aromatic ring substituent such as a cycloalkyl substituent. This precursor is preferably a compound (1) represented by formula (1-1), in which the vertex of the cage structure has a cyclohexyl (Cy). The compound (1) is preferably synthesized by nuclear hydrogenation in the presence of a noble metal catalyst. TIFF2025125602000008.tif5195

[0026] The organosilicon compounds of the present invention can be synthesized using compound (1) in a one-step synthesis via reaction with a chlorosilyl compound having a dichlorosilyl or trichlorosilyl group or tetrachlorosilane, or in a two-step synthesis via reaction with methyldichlorosilane followed by hydrosilylation with a compound having an unsaturated hydrocarbon group. By providing functional groups or groups having functional groups to these chlorosilyl compounds or compounds having unsaturated hydrocarbon groups, organosilicon compounds having functional groups or groups having functional groups can be synthesized. Commercially available chlorosilyl compounds may be used, or those synthesized by known techniques, such as the reaction of a halogenated silane with a Grignard reagent, may be used.

[0027] 2. Polymer of the Present Invention When the functional group of the organosilicon compound of the present invention is an addition-polymerizable or condensation-polymerizable group, the polymer of the present invention can be obtained by a general polymerization method such as radical polymerization, anionic polymerization, cationic polymerization, metal-initiated polymerization, or condensation polymerization. In this case, a single monomer may be used, or copolymerized with other monomers. Copolymers obtained by arranging multiple monomers may be random copolymers, block copolymers, or alternating copolymers. Graft copolymers can also be obtained by graft copolymerization with other polymers.

[0028] In the polymerization reaction for synthesizing the polymer of the present invention, it is preferable to use a solvent. There are no particular limitations on the solvent as long as it can dissolve the raw material monomers used in the polymerization reaction or the product polymer. Examples of the solvent used in the polymerization reaction include organic solvents made of the compounds exemplified below. Examples of solvents used in polymerization reactions such as condensation polymerization reactions, radical polymerization reactions, and anionic polymerization reactions include toluene, xylene, mesitylene, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, isopropanol, propylene glycol monomethyl ether, ethyl acetate, butyl acetate, propylene glycol monomethyl acetate, N-methyl-2-pyrrolidone, formamide, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylimidazolidinone, dimethyl sulfoxide, hexamethylphosphoric triamide, sulfolane, γ-butyrolactone, tetrahydrofuran, dioxane, ethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates such as diethylene glycol mono-n-butyl ether acetate, dichloromethane, chloroform, and 1,2-dichloroethane. The optimum solvent varies depending on the polymerization reaction, but preferred examples include toluene, cyclohexanone, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, tetrahydrofuran, and diethylene glycol mono-n-butyl ether acetate, which are highly versatile. These solvents may be used alone or in combination.

[0029] The polymer of the present invention may be used as a liquid polymer or a solid polymer after removing the reaction solvent, but from the viewpoint of shortening the time required for processing the polymer, such as film formation, it is preferable to leave the reaction solvent intact and use the polymer as a polymer solution or gel. [Example]

[0030] The present invention will be explained in more detail below by way of synthesis examples and examples for synthesizing the precursor of the organosilicon compound of the present invention, the organosilicon compound of the present invention, and the polymer of the present invention, but the present invention is not limited to these examples in any way. The names of compounds, trade names, etc. corresponding to the abbreviations used in the synthesis examples and examples are listed below. <Functional group> Cy: Cyclohexyl Ph: Phenyl Me: Methyl Ac: Acetyl <Solvent> THF: tetrahydrofuran DEF: N,N-diethylformamide <Reagents> XQ1175: Compound (1') represented by formula (1-1') (XQ1175; trade name; manufactured by JNC Corporation) TIFF2025125602000009.tif4176XQ1066: Compound (2') represented by formula (1-2') (XQ1066; trade name; manufactured by JNC Corporation) TIFF2025125602000010.tif4181

[0031] The abbreviations for the measurement items in the examples are shown below. Mn: Number average molecular weight Mw: Weight average molecular weight

[0032] Next, the measuring devices and analytical conditions used in the synthesis examples and working examples are shown below. <ft-ir> Equipment: JASCO FT / IR-6700V Measurement conditions: KBr method, room temperature < 1 H-NMR Equipment: JEOL Ltd. JNM-ECZ500R (500MHz) Solvent: deuterated chloroform Measurement temperature: room temperature < 29 Si-NMR Equipment: JEOL Ltd. JNM-ECZ500R (500MHz) Solvent: deuterated chloroform Measurement temperature: room temperature <gpc> Equipment: High-performance liquid chromatograph system CO-2065Plus manufactured by JASCO Corporation Detector: RI-4030 Eluent:THF Flow rate: 1.0mL / min Column: Shodex KF804L manufactured by Resonac Inc. (formerly Showa Denko K.K.) (two connected in series) Column temperature: 40℃ Sample concentration: 1 wt% Injection volume: 20μl Standard sample for calibration curve: TSK standard polystyrene manufactured by Tosoh Corporation

[0033] Synthesis Example 1 <Synthesis of Compound (1): Precursor of the Organosilicon Compound of the Present Invention> In a 2 L high-pressure reactor equipped with a stirrer, compound (1') (XQ1175) (267.4 g; 250.0 mmol), Ru / C (5 wt% Ru, hydrous) (2.0 g; 1.0 mmol Ru) (manufactured by N.E. Chemcat Corporation), and cyclopentyl methyl ether (1300.0 g) were reacted at 80 °C for 3 hours under a 0.2 MPa hydrogen atmosphere. The catalyst was then filtered to separate the solid and liquid, and anhydrous magnesium sulfate was added to the filtrate for dehydration and drying. After solid-liquid separation by filtration, the filtrate was concentrated using a rotary evaporator. The resulting solid concentrate was dried under reduced pressure at 70 °C for 6 hours to obtain compound (1) as a white solid (yield: 273.8 g, 98%). GPC analysis of the resulting compound (1) confirmed a single peak, and no impurities were detected. The IR spectrum of this compound (1) is shown in Figure 1. 1 is an IR spectrum of the compound (1) represented by the above formula (1-1), which is a precursor of the organosilicon compound of the present invention synthesized in Synthesis Example 1. From the IR spectrum of FIG. 1, the aromatic ring-derived peak at 1597 cm observed in the IR spectrum of the raw material compound (1′) (FIG. 2) is observed by the nuclear hydrogenation reaction. -1 and 3016-3084 cm -1 It was confirmed that the compound (1') disappeared. Figure 2 is an IR spectrum of the compound (1') represented by the above formula (1-1'), which is the compound used in the synthesis of the compound (1) in Synthesis Example 1. The compound (1') is manufactured by JNC Corporation under the trade name of XQ1175. As a result of NMR measurement, it was confirmed that compound (1) has the structure of formula (1-1), and its chemical shifts are shown below. 1 H-NMR (500MHz, CDCl3) δ0.65-0.82 (m, 8H), 1.15-1.37 (m, 40H), 1.59-1.92 (m, 40H). 29 Si-NMR (79MHz, CDCl3) δ-60.41,-71.76. GPC analysis revealed that Mn was 780 and Mw was 805.

[0034] Example 1 <Synthesis of Compound (2), an organosilicon compound of the present invention having a hydrosilyl group> Compound (1) (67.10 g; 60.0 mmol) obtained in Synthesis Example 1, triethylamine (30.36 g; 300.0 mmol), and THF (600 g) were added to a 1 L four-neck flask equipped with a dropping funnel, thermometer, and reflux condenser. The mixture was stirred under a nitrogen atmosphere. While maintaining the solution temperature at 23-38°C, dichloromethylsilane (17.25 g; 150.0 mmol) was added dropwise using the dropping funnel over approximately 30 minutes. After the addition was complete, the mixture was heated in an oil bath with stirring and refluxed for 3 hours, after which the reaction mixture was cooled to room temperature. Next, 500 g of the reaction solvent was distilled off, and the reaction system was cooled to room temperature. Pure water (150 g) was added dropwise using the dropping funnel. After stirring for 10 minutes, the organic and aqueous layers were separated using a separatory funnel. The organic layer was washed twice with pure water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to precipitate a solid. The precipitated solid was washed with normal heptane (750 ml), filtered, and dried under reduced pressure to obtain compound (2) as a white powdery solid (yield: 71.6 g, 99.2%).

[0035] The structure of compound (2) shown in formula (1-2) was confirmed by FT-IR analysis. -1 Absorption due to Si-H stretching was confirmed. 29 As a result of Si-NMR analysis, signals of the D structure and two types of T structure were confirmed. 1 H-NMR analysis confirmed that the integral ratio of (Si)H groups, Cy groups, and Me groups was 2:88:6, respectively. GPC analysis revealed that Mn was 830 and Mw was 840.

[0036] TIFF2025125602000011.tif4170

[0037] Example 2 <Synthesis of the glycidyl group-containing organosilicon compound of the present invention: compound (3)> Compound (2) (6.01 g; 5.00 mmol) obtained in Example 1, allyl glycidyl ether (1.43 g; 12.5 mmol), and THF (60.0 g) were added to a 200 mL four-neck flask equipped with a dropping funnel, a thermometer, and a reflux condenser. The mixture was stirred under a nitrogen atmosphere and heated in an oil bath to maintain the solution temperature at 70°C. Karstedt catalyst (10.0 μl) was added using a microsyringe, and stirring was continued for 1 hour. A sample of the reaction solution was taken and subjected to FT-IR analysis, revealing a peak at 2140 cm suggesting the presence of Si-H groups. -1 After the disappearance of the peak was confirmed, the reaction system was cooled to room temperature to terminate the reaction. The reaction solution was concentrated using an evaporator to obtain compound (3) as a white solid (yield: 6.9 g, 96.5%).

[0038] When the structure of compound (3) shown in formula (1-3) was confirmed, 29 As a result of Si-NMR analysis, signals of the D structure and two types of T structure were confirmed. 1 As a result of H-NMR analysis, signals derived from (Si)Me group, Cy group, and the raw material allyl glycidyl ether were confirmed.

[0039] TIFF2025125602000012.tif41112

[0040] Example 3 <Synthesis of the hydroxyl group-containing organosilicon compound of the present invention: compound (4)> A reaction was carried out in the same manner as in Example 2, except that 2-allyloxyethanol (1.27 g; 12.4 mmol) was used instead of allyl glycidyl ether. The reaction system was cooled to room temperature to terminate the reaction, and the reaction solution was concentrated using an evaporator to obtain compound (4) as a white solid (yield: 6.85 g, 97.4%).

[0041] As in Example 2, 1 H-NMR and 29 The structure of compound (4) shown in formula (1-4) was confirmed by Si-NMR analysis.

[0042] TIFF2025125602000013.tif41112

[0043] Example 4 <Synthesis of Acetoxy Group-Containing Organosilicon Compound of the Present Invention: Compound (5)> The reaction was carried out in the same manner as in Example 2, except that 2-allyloxyethyl ester of acetate (1.80 g; 12.5 mmol) prepared from 2-allyloxyethanol and acetyl chloride was used instead of allyl glycidyl ether. After the reaction was completed by cooling the reaction system to room temperature, the reaction solution was concentrated using an evaporator to obtain compound (5) as a white solid (yield: 7.33 g, 98.4%).

[0044] As in Example 2, 1 H-NMR and 29 The structure of compound (5) shown in formula (1-5) was confirmed by Si-NMR analysis.

[0045] TIFF2025125602000014.tif41117

[0046] Example 5 <Synthesis of the carboxyl group-containing organosilicon compound of the present invention: compound (6)> A reaction was carried out in the same manner as in Example 2, except that 4-pentenoic acid trimethylsilyl ester (1.25 g; 12.5 mmol) was used instead of allyl glycidyl ether. The reaction system was cooled to room temperature to terminate the reaction, and the reaction solution was concentrated using an evaporator to obtain compound (6) as a white solid (yield: 6.90 g, 98.4%).

[0047] As in Example 2, 1 H-NMR and 29 The structure of compound (6) shown in formula (1-6) was confirmed by Si-NMR analysis.

[0048] TIFF2025125602000015.tif41105

[0049] Example 6 <Synthesis of Compound (7), an organosilicon compound of the present invention having a methacryloxy group> Compound (1) (6.71 g; 6.00 mmol) obtained in Synthesis Example 1, THF (70 g), and triethylamine (3.04 g; 30.0 mmol) were added to a 200 mL four-neck flask equipped with a dropping funnel, thermometer, and reflux condenser. The mixture was stirred under a nitrogen atmosphere. While maintaining the solution temperature at 5-10°C, methacryloxypropylmethyldichlorosilane (3.60 g; 14.93 mmol) was added dropwise using the dropping funnel over approximately 30 minutes, and the mixture was allowed to react at room temperature for 5 hours. Purified water (100 g) was added dropwise using the dropping funnel. After stirring for 10 minutes, the organic and aqueous layers were separated using a separatory funnel. The organic layer was washed twice with purified water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a pale yellow solid. The resulting pale yellow solid was purified by silica gel chromatography using a mixed solvent of normal hexane and ethyl acetate in a volume ratio of 5:1 to obtain compound (7) as a white solid (yield: 8.62 g, 98.7%).

[0050] As in Example 2, 1 H-NMR and 29 The structure of compound (7) shown in formula (1-7) was confirmed by Si-NMR analysis.

[0051] TIFF2025125602000016.tif41112

[0052] Example 7 <Synthesis of Compound (8), an organosilicon compound of the present invention having a 3-chloropropyl group> The reaction and post-treatment were carried out in the same manner as in Example 6, except that 3-chloropropylmethyldichlorosilane (2.90 g; 15.1 mmol) was used instead of methacryloxypropylmethyldichlorosilane, to obtain compound (8) as a white solid (yield: 7.95 g, 97.7%).

[0053] As in Example 2, 1 H-NMR and 29 The structure of compound (8) shown in formula (1-8) was confirmed by Si-NMR analysis.

[0054] TIFF2025125602000017.tif41101

[0055] Example 8 <Synthesis of Compound (9), an organosilicon compound of the present invention having an anilinyl group> The reaction and post-treatment were carried out in the same manner as in Example 6, except that anilinomethyldichlorosilane (3.12 g; 15.1 mmol) was used instead of methacryloxypropylmethyldichlorosilane, to obtain compound (9) as a white solid (yield: 8.25 g, 99.3%).

[0056] As in Example 2, 1 H-NMR and 29 The structure of compound (9) shown in formula (1-9) was confirmed by Si-NMR analysis.

[0057] TIFF2025125602000018.tif41108

[0058] Example 9 <Synthesis of the vinyl group-containing organosilicon compound of the present invention: compound (10)> The reaction and post-treatment were carried out in the same manner as in Example 6, except that vinylmethyldichlorosilane (2.12 g; 15.0 mmol) was used instead of methacryloxypropylmethyldichlorosilane, to obtain compound (10) as a white solid (yield: 7.45 g, 99.0%).

[0059] As in Example 2, 1 H-NMR and 29 The structure of compound (10) shown in formula (1-10) was confirmed by Si-NMR analysis.

[0060] TIFF2025125602000019.tif4192

[0061] Example 10 <Synthesis of the hydroxyl group-containing organosilicon compound of the present invention: compound (11)> The reaction and post-treatment were carried out in the same manner as in Example 6, except that methyltrichlorosilane (2.24 g; 15.0 mmol) was used instead of methacryloxypropylmethyldichlorosilane, to obtain compound (11) as a white solid (yield: 7.33 g, 99.0%).

[0062] As in Example 2, 1 H-NMR and 29 The structure of compound (11) shown in formula (1-11) was confirmed by Si-NMR analysis.

[0063] TIFF2025125602000020.tif4174

[0064] Example 11 <Synthesis of the cyano group-containing organosilicon compound of the present invention: compound (12)> The reaction and post-treatment were carried out in the same manner as in Example 6, except that (cyanoethyl)methyldichlorosilane (2.52 g; 15.0 mmol) was used instead of methacryloxypropylmethyldichlorosilane, to obtain compound (12) as a white solid (yield: 7.33 g, 93.3%).

[0065] As in Example 2, 1 H-NMR and 29 The structure of compound (12) shown in formula (1-12) was confirmed by Si-NMR analysis.

[0066] TIFF2025125602000021.tif4185

[0067] Example 12 <Synthesis of Compound (13), an organosilicon compound of the present invention having an acryloxy group> The reaction and post-treatment were carried out in the same manner as in Example 6, except that (3-acryloyloxypropyl)methyldichlorosilane (3.42 g; 15.1 mmol) was used instead of methacryloxypropylmethyldichlorosilane, to obtain compound (13) as a white solid (yield: 8.50 g, 99.3%).

[0068] As in Example 2, 1 H-NMR and 29 The structure of compound (13) shown in formula (1-13) was confirmed by Si-NMR analysis.

[0069] TIFF2025125602000022.tif41112

[0070] Example 13 <Synthesis of dichloro-containing organosilicon compound of the present invention: compound (14)> A 200 mL three-neck flask equipped with a dropping funnel, reflux condenser, and thermometer was charged with compound (1) (6.71 g; 6.00 mmol) obtained in Synthesis Example 1, triethylamine (3.04 g; 30.0 mmol), and ultra-dehydrated THF (70 g) and sealed with dry nitrogen. Tetrachlorosilane (2.56 g; 15.1 mmol) was slowly added dropwise at room temperature while stirring with a magnetic stirrer. The mixture was then stirred at room temperature for 3 hours. The resulting ammonium chloride was removed from the reaction mixture by filtration, and the mixture was concentrated under reduced pressure to remove unreacted tetrachlorosilane and the solvent THF. The resulting residue was washed with ultra-dehydrated hexane and dried to obtain compound (14) as a white solid (yield: 7.80 g, 99.1%).

[0071] When the structure of compound (14) shown in formula (1-14) was confirmed, 29 As a result of Si-NMR analysis, signals of the D structure and two types of T structure were confirmed. 1 As a result of 1 H-NMR analysis, only the signal of the Cy group was confirmed.

[0072] TIFF2025125602000023.tif4196

[0073] Example 14 <Synthesis of Compound (15): Organosilicon Compound Having a Carboxylic Acid Anhydride Residue> A 200 mL three-neck flask equipped with a reflux condenser and a thermometer was charged with compound (2) (6.0 g; 5.00 mmol) obtained in Example 1, allylsuccinic anhydride (1.75 g; 12.49 mmol), and ultra-dehydrated THF (60 g), and the flask was sealed with dry nitrogen. The mixture was heated to reflux temperature while stirring with a magnetic stirrer, and Karstedt catalyst (40.0 μL) was added using a microsyringe. After stirring for 7 hours at reflux temperature, a sample was taken and subjected to FT-IR analysis, revealing a peak at 2140 cm indicating the presence of Si-H groups. -1 After the disappearance of the peak was confirmed, the reaction system was cooled to room temperature to terminate the reaction. The reaction solution was concentrated using an evaporator, and the resulting residue was washed with methanol (150.0 g). After filtration and drying, compound (15) was obtained as a white solid (yield: 7.3 g, 98.9%).

[0074] As in Example 2, 1 H-NMR and 29 The structure of compound (15) shown in formula (1-15) was confirmed by Si-NMR analysis.

[0075] TIFF2025125602000024.tif41108

[0076] Example 15 <Synthesis of the amino group-containing organosilicon compound of the present invention: compound (16)> The reaction and post-treatment were carried out in the same manner as in Example 6, except that 3-(dichloromethylsilyl)propan-1-amine (2.60 g; 15.1 mmol) was used instead of methacryloxypropylmethyldichlorosilane, to give compound (16) as a white solid (yield: 7.79 g, 98.6%).

[0077] As in Example 2, 1 H-NMR and 29 The structure of compound (16) shown in formula (1-16) was confirmed by Si-NMR analysis.

[0078] TIFF2025125602000025.tif41103

[0079] Example 16 <Synthesis of Compound (17), an organosilicon compound of the present invention having a 1,3-dimethyldisiloxane-1,3-diyl group> The reaction and post-treatment were carried out in the same manner as in Example 6, except that 1,3-dichloro-1,3-dimethyldisiloxane (2.62 g; 15.0 mmol) was used instead of methacryloxypropylmethyldichlorosilane, to obtain compound (17) as a white solid (yield: 7.90 g, 99.5%).

[0080] As in Example 2, 1 H-NMR and 29 The structure of compound (17) shown in formula (1-17) was confirmed by Si-NMR analysis. GPC analysis revealed that Mn was 950 and Mw was 1,010.

[0081] TIFF2025125602000026.tif46110

[0082] Example 17 <Synthesis of tetrahydroxyl-containing organosilicon compound of the present invention: compound (18)> Compound (14) (5.0 g) obtained in Example 13 was dissolved in THF (25.0 g), and purified water (10 g) was added dropwise. After stirring for 10 minutes, the organic and aqueous layers were separated using a separatory funnel. The organic layer was washed twice with purified water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a pale yellow solid. The obtained pale yellow solid was purified by silica gel chromatography using a 5:1 volume ratio of normal hexane-ethyl acetate mixed solvent to obtain compound (18) represented by formula (1-18) (yield: 4.5 g, 90.0%).

[0083] TIFF2025125602000027.tif46110

[0084] As in Example 2, 1 H-NMR and 29 The structure of compound (18) shown in formula (1-18) was confirmed by Si-NMR analysis.

[0085] Example 18 <Synthesis of Compound (19), an Organosilicon Compound of the Present Invention Having a 7-Oxabicyclo[4.1.0]heptan-3-yl Group> The reaction and post-treatment were carried out in the same manner as in Example 6, except that compound (18) (3.72 g; 3.0 mmol) was used instead of compound (1) and (2-(7-oxabicyclo[4.1.0]heptan-3-yl)ethyl)chlorodimethylsilane (3.20 g; 14.6 mmol) was used instead of methacryloxypropylmethyldichlorosilane, to give compound (19) as a white solid (yield: 5.80 g, 98.1%).

[0086] As in Example 2, 1 H-NMR and 29 The structure of compound (19) shown in formula (1-19) was confirmed by Si-NMR analysis.

[0087] TIFF2025125602000028.tif56155

[0088] Example 19 <Synthesis of the Polymer of the Present Invention: Polysiloxane (Polymer (20))> Organosilicon compound (2) (5 g) obtained by the synthesis method of Example 1, toluene (120 g), and a mixed solution (0.05 g) of n-hexylamine / 2-ethylhexanoic acid (molar ratio 1:2) were added to a 200 mL flask equipped with a reflux condenser and a stirrer. The mixture was heated in an oil bath under reflux with stirring under a nitrogen atmosphere for 16 hours. The mixture was then cooled to room temperature, filtered, and concentrated under reduced pressure using an evaporator to obtain a white solid polysiloxane (polymer (20)). GPC analysis of the resulting white solid revealed an Mn of 2,200 and an Mw of 4,300.

[0089] Example 20 <Synthesis of the Polymer of the Present Invention: Polysiloxane (Polymer (21))> A 200 mL flask equipped with a reflux condenser, a stirrer, and a Dean-Stark tube filled with molecular sieves 3A was charged with 5 g of the organosilicon compound (2) obtained by the synthesis method in Example 1 and 120 g of toluene. Furthermore, 0.05 g of p-toluenesulfonic acid monohydrate was added. The mixture was heated in an oil bath under reflux with stirring under a nitrogen atmosphere for 24 hours. After cooling to room temperature, the mixture was repeatedly separated and washed with saturated aqueous sodium bicarbonate and ion-exchanged water until neutral. The resulting organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure using an evaporator to obtain a white solid polysiloxane (polymer (21)). GPC analysis of the resulting white solid revealed an Mn of 3,800 and an Mw of 8,600.

[0090] Example 21 <Synthesis of the Polymer of the Present Invention: Polysiloxane (Polymer (22))> A 200 mL flask equipped with a reflux condenser and a stirrer was charged with organosilicon compound (2) (13.5 g) obtained by the synthesis method in Example 1, tetradecamethyldivinylheptasiloxane (5.6 g), and toluene (80 g). The mixture was stirred under a nitrogen atmosphere and heated in an oil bath to maintain the solution temperature at 70°C. Karstedt catalyst (12.0 μL) was then added using a microsyringe. 1 The reaction was terminated by confirming the disappearance of the vinyl group peak (5.79-6.06 ppm) by H-NMR. After concentrating under reduced pressure using an evaporator, the mixture was diluted with acetone, activated carbon (0.5 g) was added, and the mixture was stirred overnight at room temperature. After pressure filtration using a 0.2 μm filter, the mixture was concentrated under reduced pressure using an evaporator to obtain a colorless, syrup-like polysiloxane (polymer (22)). GPC analysis of the resulting syrup-like substance revealed that Mn was 4,700 and Mw was 10,300.

[0091] Example 22 <Synthesis of the Polymer of the Present Invention: Polysiloxane (Polymer (23))> Organosilicon compound (7) (5 g) obtained by the synthesis method of Example 6, glycidyl methacrylate (28 g), 3-methacryloxypropyltrimethoxysilane (28 g), 2,2'-azobis(methyl isobutyrate) (20.0 g), and diethylene glycol mono-n-butyl ether acetate (90 g) were added to a four-neck 300 mL flask equipped with a stirrer, and the mixture was heated at a polymerization temperature of 105°C for 4 hours to polymerize. The reaction solution was cooled to room temperature, yielding a solution of polysiloxane (polymer (23)). A portion of the solution was sampled and analyzed by GPC, which revealed that the Mn was 5,050 and the Mw was 12,010.

[0092] Example 23 <Synthesis of the Polymer of the Present Invention: Polysiloxane (Polymer (24))> A 100 mL flask equipped with a reflux condenser and a stirrer was charged with 5 g of the organosilicon compound (10) obtained by the synthesis method of Example 9, 5 g of tetramethylhexaphenylpentasiloxane, 5 g of compound (2') (XQ1066), and 50.0 g of toluene. The mixture was stirred under a nitrogen atmosphere and heated in an oil bath to maintain the solution temperature at 70°C. Karstedt catalyst (10.0 μl) was added via a microsyringe, and stirring was continued for 1 hour. The mixture was then cooled to room temperature, yielding a solution of polysiloxane (polymer (24)). A portion of the solution was sampled and analyzed by GPC, revealing that the Mn was 13,200 and the Mw was 42,850.

[0093] Example 24 <Synthesis of the Polymer of the Present Invention: Polyamic Acid (Polymer (25))> A 200 mL four-neck separable flask equipped with a thermometer and stirrer was charged with 15.8 g of the organosilicon compound (9) obtained by the synthesis method of Example 8 and 71 g of dehydrated N-methyl-2-pyrrolidone as a reaction solvent. After the solids had completely dissolved, the mixture was placed under a nitrogen atmosphere at room temperature. 2.0 g of pyromellitic anhydride (tetracarboxylic dianhydride) was added. After stirring for 16 hours, 88.8 g of a homogeneous, transparent solution of polyamic acid (polymer (25)) with a solids concentration of 20.0 wt % was obtained. A portion of the solution was sampled and analyzed by GPC. The Mn was 85,300 and the Mw was 185,000.

[0094] Example 25 <Synthesis of the Polymer of the Present Invention: Polyimide (Polymer (26))> 15 mL of the polyamic acid (polymer (25)) solution was taken with a micropipette and applied to a cleaned silicon substrate in a square area of ​​at least 10 cm x 10 cm using an applicator. The substrate was then placed on a hot plate at 80°C for 30 minutes to evaporate the solvent, and heated in an oven at 150°C for 15 minutes. The oven temperature was then raised to 350°C over an hour, and the substrate was further heated at 350°C for 30 minutes for full curing (baking), yielding a transparent polyimide (polymer (26)) in the form of a cured film with a thickness of 200 μm.

[0095] Example 26 <Synthesis of the Polymer of the Present Invention: Polyester (Polymer (27))> A 200 mL four-neck separable flask equipped with a thermometer, stirrer, and nitrogen inlet tube was charged with 15.6 g of the organosilicon compound (6) obtained by the synthesis method of Example 5, 69.0 g of toluene, 1.6 g of 1,4-butanediol, and 0.05 g of titanium triisopropoxide, and the mixture was heated and stirred at 220°C for 1 hour. After cooling to room temperature, 86.25 g of a homogeneous, transparent solution of polyester (polymer (27)) with a solids concentration of 20.0 wt% was obtained. A portion of the solution was sampled and analyzed by GPC, revealing an Mn of 4,530 and an Mw of 14,020.

[0096] Example 27 <Synthesis of the Polymer of the Present Invention: Polyester (Polymer (28))> A 200 mL four-neck separable flask equipped with a thermometer, stirrer, and nitrogen inlet tube was charged with 15.6 g of the organosilicon compound (6) obtained by the synthesis method of Example 5, 90 g of dehydrated N-methyl-2-pyrrolidone, 1.0 g of 1,4-butanediol, 2.4 g of bis(aminomethyl)norbornane, and 3.5 g of pyromellitic anhydride, and heated with stirring at 180°C for 3 hours. After cooling to room temperature, 112 g of a homogeneous, transparent solution of polyester (polymer (28)) with a solids concentration of 20.0 wt% was obtained. A portion of the solution was sampled and analyzed by GPC, revealing an Mn of 10,530 and an Mw of 14,020.

[0097] Example 28 <Synthesis of the Polymer of the Present Invention: Polyurea (Polymer (29))> Under a nitrogen atmosphere, a 100 mL three-neck flask equipped with a reflux condenser, thermometer, and dropping funnel was charged with 7.5 g of the organosilicon compound (16) obtained by the synthesis method of Example 15 and 34.5 g of DEF. The mixture was then cooled to 5°C in an ice bath, and 1.1 g of 1,5-pentamethylene diisocyanate was slowly added dropwise via syringe. The ice bath was then removed and the mixture was allowed to return to room temperature. The mixture was then heated to 50°C in an oil bath and stirred. After cooling to room temperature, 43.1 g of a homogeneous, transparent solution of polyurea (polymer (29)) with a solids concentration of 20.0 wt% was obtained. A portion of the solution was sampled and analyzed by GPC, revealing an Mn of 10,530 and an Mw of 22,500. [Industrial Applicability]

[0098] The organosilicon compound of the present invention provides a silsesquioxane structure having a non-aromatic ring substituent at the apex of the cage structure. In the organosilicon compound of the present invention, by converting the terminal functional groups of the silsesquioxane structure having a non-aromatic ring substituent at the apex of the cage structure to functional groups such as amino groups, hydrosilyl groups, glycidyl groups, hydroxyl groups, acetoxy groups, carboxyl groups, methacryloxy groups, chloropropyl groups, vinyl groups, and siloxane groups, it is possible to obtain precursors of the polymers of the present invention that are useful in the development of useful optical components, dielectric materials, electronic component materials, and the like, and the structure having a non-aromatic ring substituent at the apex of the cage structure is extremely useful.< / gpc>

Claims

1. An organosilicon compound represented by formula (1): In formula (1), R is independently hydrogen, halogen, alkyl having 1 to 45 carbon atoms, or cycloalkyl having 4 to 18 carbon atoms; in the alkyl having 1 to 45 carbon atoms, at least one hydrogen may be replaced by fluorine, and at least one -CH ２ - may be replaced by -O- or cycloalkylene having 4 to 18 carbon atoms, and in the cycloalkyl having 4 to 18 carbon atoms, at least one hydrogen may be replaced by fluorine or alkyl having 1 to 3 carbon atoms; Y is a group selected from the groups represented by formula (2-1) or formula (2-2), and two Ys may be the same group or different groups; In formula (2-1), R １ is alkyl having 1 to 45 carbon atoms, aryl having 6 to 45 carbon atoms, or arylalkyl having 7 to 45 carbon atoms; in the alkyl having 1 to 45 carbon atoms, at least one hydrogen may be replaced by fluorine, and at least one —CH ２ - may be replaced by -O-, -CH=CH-, cycloalkylene having 4 to 18 carbon atoms or cycloalkenylene having 4 to 18 carbon atoms; in the aromatic ring of the aryl having 6 to 45 carbon atoms and the arylalkylene having 7 to 45 carbon atoms, at least one hydrogen may be replaced by fluorine; in the alkylene of the arylalkyl having 7 to 45 carbon atoms, the number of carbon atoms is 1 to 39 and at least one -CH ２ - may be replaced by -O-, -CH=CH- or cycloalkylene; and Z is R １ It is a group, functional group or group having a functional group having the same definition as above. In formula (2-2), Q is —O—, —CH ２ - or a single bond. １ is R １ a group, functional group or group having a functional group having the same definition as １ may be the same group or may be composed of different groups.

2. In formula (1) and formula (2-1), R １ 2. The organosilicon compound of claim 1, wherein is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, or phenyl.

3. In the formula (1) according to claim 1, R is independently alkyl having 1 to 12 carbon atoms or cycloalkyl having 4 to 10 carbon atoms; in the alkyl having 1 to 12 carbon atoms, at least one hydrogen may be replaced by fluorine, and at least one -CH ２ The organosilicon compound according to claim 2, wherein - may be replaced by -O- or a cycloalkylene having 4 to 10 carbon atoms, and in the cycloalkyl having 4 to 10 carbon atoms, at least one hydrogen may be replaced by a fluorine atom or an alkyl having 1 to 3 carbon atoms.

4. The organosilicon compound according to claim 2, wherein in formula (1) of claim 1, R is independently a cycloalkyl having 4 to 10 carbon atoms; in the cycloalkyl having 4 to 10 carbon atoms, at least one hydrogen may be replaced by fluorine or an alkyl having 1 to 3 carbon atoms; and when the cycloalkyl in which at least one hydrogen is replaced by fluorine or an alkyl having 1 to 3 carbon atoms has multiple substituents, these substituents may be the same or different groups.

5. The organosilicon compound according to claim 2, wherein in formula (1) according to claim 1, all R are the same group selected from cycloalkyl having 4 to 10 carbon atoms; in the cycloalkyl having 4 to 10 carbon atoms, at least one hydrogen may be replaced by fluorine or alkyl having 1 to 3 carbon atoms, and when the cycloalkyl in which at least one hydrogen is replaced by fluorine or alkyl having 1 to 3 carbon atoms has multiple substituents, these substituents may be the same group or different groups.

6. The organosilicon compound according to claim 2, wherein in formula (1) according to claim 1, all R are the same group selected from cycloalkyl having 4 to 10 carbon atoms in which at least one hydrogen may be replaced by fluorine or alkyl having 1 to 3 carbon atoms, and when the cycloalkyl in which at least one hydrogen is replaced by fluorine or alkyl having 1 to 3 carbon atoms has multiple substituents, these substituents may be the same group or different groups.

7. 3. The organosilicon compound according to claim 2, wherein in formula (1) of claim 1, all R are cyclohexyl.

8. In formula (1) and formula (2-1) or formula (2-2), R １ is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, or phenyl; and Z or Z １ is a functional group or a group having a functional group, the functional group being a group directly bonded to the Si atom and selected from hydrogen, halogen, —OH, alkoxy, alkenyl and fluorinated alkyl, the group having a functional group being a group composed of a divalent group and a functional group bonded to the Si atom via the divalent group, the divalent group being a divalent group selected from alkylene, alkylcycloalkylene, alkylenephenylene, alkylphenylene and alkylphenylalkylene, and the alkylene and alkyl in these divalent groups each having at least one —CH ２ - may be replaced by -O-, and the functional group bonded to the Si atom via a divalent group is hydrogen, halogen, -OH, fluorinated alkyl, alkoxy, carboxyl, 2-oxapropanedioyl, carboxylic anhydride residue, maleimide residue, acetoxy, vinyloxycarbonyl, allyloxycarbonyl, acryloyloxy, methacryloyloxy, polyalkyleneoxy, oxiranyl, 3,4-epoxycyclohexyl, oxetanyl, alkenyl, cycloalkenyl, -NH ２ , -CN, -NCO, -SH and -PH ２ 2. The organosilicon compound of claim 1, wherein the group is selected from the group consisting of:

9. In the formula (1) according to claim 1, R is independently alkyl having 1 to 12 carbon atoms or cycloalkyl having 4 to 10 carbon atoms; in the alkyl having 1 to 12 carbon atoms, at least one hydrogen may be replaced by fluorine, and at least one -CH ２ The organosilicon compound according to claim 8, wherein - may be replaced by -O- or a cycloalkylene having 4 to 10 carbon atoms, and in the cycloalkyl having 4 to 10 carbon atoms, at least one hydrogen may be replaced by a fluorine atom or an alkyl having 1 to 3 carbon atoms.

10. The organosilicon compound according to claim 8, wherein in formula (1) of claim 1, R is independently a cycloalkyl having 4 to 10 carbon atoms; in the cycloalkyl having 4 to 10 carbon atoms, at least one hydrogen may be replaced by fluorine or an alkyl having 1 to 3 carbon atoms; and when the cycloalkyl in which at least one hydrogen is replaced by fluorine or an alkyl having 1 to 3 carbon atoms has multiple substituents, these substituents may be the same or different groups.

11. The organosilicon compound according to claim 8, wherein in formula (1) according to claim 1, all R are the same group selected from cycloalkyl having 4 to 10 carbon atoms; in the cycloalkyl having 4 to 10 carbon atoms, at least one hydrogen may be replaced by fluorine or alkyl having 1 to 3 carbon atoms, and when the cycloalkyl in which at least one hydrogen is replaced by fluorine or alkyl having 1 to 3 carbon atoms has multiple substituents, these substituents may be the same group or different groups.

12. The organosilicon compound according to claim 8, wherein in formula (1) according to claim 1, all R are the same group selected from cycloalkyl having 4 to 10 carbon atoms in which at least one hydrogen may be replaced by fluorine or alkyl having 1 to 3 carbon atoms, and when the cycloalkyl in which at least one hydrogen is replaced by fluorine or alkyl having 1 to 3 carbon atoms has multiple substituents, the substituents may be the same group or different groups.

13. 9. The organosilicon compound according to claim 8, wherein in formula (1) of claim 1, all R are cyclohexyl.

14. In the formula (1) and the formula (2-1) or the formula (2-2), Z or Z １ The organosilicon compound according to any one of claims 1 to 13, wherein is a fluorinated alkyl or a group having a fluorinated alkyl.

15. In the formula (1) and the formula (2-1) or the formula (2-2), Z or Z １ is alkenyl, or alkenyl, —OH, carboxyl, 2-oxapropanedioyl, oxiranyl, 3,4-epoxycyclohexyl, oxetanyl, and —NH ２ The organosilicon compound according to any one of claims 1 to 13, wherein the compound is a group having any one of the following formulas:

16. A polymer obtainable by using the organosilicon compound according to claim 15.

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