JP2010120901A - Completely fused oligosilsesquioxane stereoisomer, polymer using the same and method for producing them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer obtained by the processes of separating (isolating) a double decker ring closure type T<SB>8</SB>trans/cis isomer mixture each singly, or separating so that one of the isomers becomes excessive by a re-crystallization treatment and then polymerizing by using the above, and a method for producing the same. <P>SOLUTION: This trans or cis isomer of a completely fused oligosilsesquioxane is expressed by general formula (1) [wherein, Rs are each independently H, 1-10C alkyl of which optional number of hydrogen atoms may be replaced with 1-10C alkyl, 6-10C aryl, 7-10C arylalkyl or 3-10C cycloalkyl which may be substituted by a halogen atom or 1-10C alkyl; and X is 4C saturated branched alkyl]. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a fully condensed oligosilsesquioxane stereoisomer, a polymer using the same, and a method for producing them.

Polysilsesquioxane is an intermediate substance between inorganic silica [SiO ₂ ] and organic silicone [(R ₂ SiO) _n ] and is represented by (RSiO _3/2 ) _n . The inorganic structure portion having a siloxane bond bears properties as an inorganic material such as excellent transparency, heat resistance, hardness, and insulation. On the other hand, the organic structure part consists of organic functional groups directly bonded to silicon atoms. Solubility and dispersion stability in organic materials, which tend to be insufficient only with an inorganic structure, adjustment of refractive index and dielectric constant, imparting photocurability It bears the characteristics such as. As described above, polysilsesquioxane having characteristics of an inorganic material and an organic material is attracting attention as an organic / inorganic hybrid material.

Polysilsesquioxane is known to have a random structure, a polyhedral structure, and a ladder structure depending on its structure. Among them, polyhedral oligosilsesquioxane (POSS) having a structure in which a Si—O bond is three-dimensionally closed has high heat resistance, oxidation resistance, chemical resistance and high mechanical properties because of its unique three-dimensional structure. It has many excellent features, such as mechanical strength and insulation, and is expected to be applied to electronic and optical materials. Among POSS, a T ₈ compound ([RSiO _3/2 ] ₈ ; T structure indicates RSiO _3/2 ), which is a fully condensed oligosilsesquioxane having a silicon atom at the top of a cube and an oxygen atom between them. Since it can be synthesized in high yield and is easily available, many reports have been made so far, and it has been used for the study of expression of new functions and improvement of functionality.

各ケイ素原子に結合する置換基全てが同じ、もしくは半分程度が同じＴ_８化合物については、比較的容易に合成でき、報告もされている（例えば、非特許文献１）。また、Ｔ_８の一つの頂点が欠けているＴ_７をクロロシラン等で閉環させたＴ_８は、８つの置換基のうち７つが同じ種類となる（例えば、非特許文献２、非特許文献３）。これらＴ_８を主鎖や側鎖にもつポリマーの合成も多数報告されている。

For all substituents attached to each silicon atom are the same, or about half the same T ₈ compounds, relatively easy to synthesize, it has also been reported (e.g., Non-Patent Document 1). Further, T ₈ in which T ₇ lacking one apex of T ₈ is closed with chlorosilane or the like has ₇ of the 8 substituents of the same type (for example, Non-Patent Document 2 and Non-Patent Document 3). . These T ₈ have been reported backbone or synthesis of the polymer having in the side chain.

Recently, and T ₈ in which Si-O bonds of the facing two places T ₈ is called double-decker type cleaved, which T ₈ of double-decker closed type which is closed at dichlorosilane are combined (e.g., Patent Documents 1, Patent Document 2), and a polymer is obtained by polymerization (for example, Non-Patent Document 4, Non-Patent Document 5, Non-Patent Document 6). Many polymerization processes of these T ₈ and double-decker closed type T _8, a polyaddition reaction such as hydrosilylation (for example, Patent Document 3, Non-Patent Document 1, Non-Patent Documents 2 and 7).

When the substituent R ′ is different from R ″ in the double-decker ring-closing type T ₈ , there are two types of isomers, a cis isomer and a trans isomer. However, no separation or selective synthesis of trans / cis isomer mixtures has been reported. Further, since the monomer is a trans / cis isomer mixture, the structure of the target compound is difficult to reflect on the physical properties and functions.
WO 2003/024870 WO 2004/024741 JP-A-2006-22207 Journal of Materials Chemistry 2005, 15, 35-36, 3725-3744 Macromolecules 1996, 29, 22, 7302-7304 Macromolecules 2005, 38, 4, 1264-1270 Macromolecules 2006, 39, 10, 3473-3475 Macromolecules 2007, 40, 16, 5698-5705 Macromolecules 2008, 41, 10, 3483-1487 Journal of American Chemical Society 1998, 120, 33, 8380-8391

The primary structure of a polymer greatly affects its higher order structure, and as a result, various physical properties such as solubility and crystallinity of the polymer are greatly changed. For example, in the case of gutta percha, which is a trans polyisoprene, and natural rubber, which is a cis polyisoprene, the primary structure has an effect on the physical properties of the polymer. In addition, it is known that polypropylene has various physical properties depending on stereoregularity.

The double-decker ring-closing T ₈ trans isomer and cis isomer can be separated. When used as a monomer for polymerization, the geometric isomerism of the monomer can be reduced to the molecular weight and thermophysical properties of the polymer compared to the trans / cis isomer mixture. It can be reflected.

In the present invention, the trans / cis isomer mixture of the double-decker ring-closing type T ₈ is separated (isolated) by recrystallization, respectively, or separated so that one of the isomers is excessive, and used. It is intended to provide a polymer obtained by polymerization and a method for producing the polymer.

That is, the present inventors introduced a sterically bulky substituent into one of the double-decker ring-closing type T ₈ , so that an excess of geometric isomers can be obtained from the trans / cis isomer mixture by recrystallization. It was found that they can be separated (isolated). Furthermore, as a result of the said different material elements obtained by siloxane copolymerized, reflecting the geometrical isomerism of the double-decker closed type T ₈ to obtain a degree of polymerization of different polymers, such as thermal decomposition temperature and glass transition temperature of the obtained polymer thermal The present inventors completed the present invention by finding that the physical properties are also different from those of the polymer derived from the trans / cis isomer mixture.

The present invention relates to general formula (1) or general formula (2).

(In the formula, each R is independently a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a cycloalkyl group. The alkyl group has 1 to 10 carbon atoms, and any hydrogen atom is a halogen atom or The aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, and the aryl group may have 6 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms. The arylalkyl group has 7 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms, and the cycloalkyl group has 3 to 10 carbon atoms. And any hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 10 carbon atoms, wherein X is It refers to a saturated branched alkyl group of prime 4.)
(2) is a trans and / or cis stereoisomer of a fully condensed oligosilsesquioxane represented by formula (1).

In the general formula (1) or the general formula (2), the present invention provides a trans and / or cis steric structure of the fully condensed oligosilsesquioxane according to claim 1, wherein R is a phenyl group. Isomer (Claim 2).

Further, the present invention provides the trans of the fully condensed oligosilsesquioxane according to claim 1 or 2, wherein X is an isobutyl group in the general formula (1) or the general formula (2). And / or a cis stereoisomer (Claim 3).

Next, the present invention relates to general formula (1) and general formula (2).

(In the formula, each R is independently a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a cycloalkyl group. The alkyl group has 1 to 10 carbon atoms, and any hydrogen atom is a halogen atom or The aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, and the aryl group may have 6 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms. The arylalkyl group has 7 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms, and the cycloalkyl group has 3 to 10 carbon atoms. And any hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 10 carbon atoms, wherein X is It refers to a saturated branched alkyl group of prime 4.)
4. The trans and / or cis of the fully condensed oligosilsesquioxane according to claim 1, wherein each isomer is separated by recrystallization from a trans / cis isomer mixture represented by A method for producing a cis stereoisomer (Claim 4).

In the present invention, the solvent for the recrystallization treatment is a saturated aliphatic hydrocarbon having 6 to 10 carbon atoms, benzene, an aromatic hydrocarbon having 7 to 12 carbon atoms including a saturated alkyl group, or a halogen having 1 to 3 carbon atoms. 5. A process for producing a trans and / or cis stereoisomer of a fully condensed oligosilsesquioxane according to claim 4, which is selected from activated aliphatic hydrocarbons (claim 5).

Furthermore, the present invention provides a transcondensation of a fully condensed oligosilsesquioxane according to any one of claims 4 to 5, wherein the temperature of the recrystallization treatment is selected from a temperature between 30 ° C and minus 80 ° C. And / or a method for producing a cis stereoisomer (Claim 6).

Next, the present invention relates to general formula (3) or general formula (4).

(In the formula, each R is independently a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a cycloalkyl group. The alkyl group has 1 to 10 carbon atoms, and any hydrogen atom is a halogen atom or The aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, and the aryl group may have 6 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms. The arylalkyl group has 7 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms, and the cycloalkyl group has 3 to 10 carbon atoms. And any hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 10 carbon atoms, and X is Saturated branched alkyl group of prime 4, n is an integer from 0 to 9, R ¹ is each independently an alkyl group. The number of carbon atoms in the alkyl group is from 1 to 10, any hydrogen atom (It may be substituted with a halogen atom or an alkyl group having 1 to 10 carbon atoms.)
A silicon compound or a polymer thereof characterized by comprising a structural unit represented by (7).

Moreover, this invention is a silicon compound or its polymer of Claim 7 characterized by R being a phenyl group in General formula (3) or General formula (4) (Claim 8).

Furthermore, the present invention provides the silicon compound or polymer thereof according to any one of claims 7 to 8, wherein in the general formula (3) or the general formula (4), X is an isobutyl group. (Claim 9).

Next, the present invention provides the silicon compound according to any one of claims 7 to 9, wherein R ¹ is a methyl group in the general formula (3) or the general formula (4). (Claim 10).

Further, in the present invention, the repeating unit of the structural unit of the general formula (3) or the general formula (4) is 1 to 1000, or the silicon compound according to any one of claims 7 to 10, A polymer (claim 11).

Furthermore, the present invention relates to general formula (1) or general formula (2).

(In the formula, each R is independently a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a cycloalkyl group. The alkyl group has 1 to 10 carbon atoms, and any hydrogen atom is a halogen atom or The aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, and the aryl group may have 6 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms. The arylalkyl group has 7 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms, and the cycloalkyl group has 3 to 10 carbon atoms. And any hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 10 carbon atoms, wherein X is It refers to a saturated branched alkyl group of prime 4.)
A trans and / or cis stereoisomer of a fully condensed oligosilsesquioxane represented by general formula (5):

(In the formula, n is an integer of 0 to 9, and R ¹ is each independently an alkyl group. The alkyl group has 1 to 10 carbon atoms, and any hydrogen atom is a halogen atom or 1 carbon atom. To 10 alkyl groups.)
The method for producing a silicon compound or a polymer thereof according to any one of claims 7 to 11, wherein the reaction is carried out in the presence or absence of a Lewis acid catalyst and a reaction solvent. (Claim 12).

Next, according to the present invention, the Lewis acid catalyst comprises an aluminum halide such as aluminum fluoride (III), aluminum chloride (III), aluminum bromide (III), aluminum iodide (III); boron fluoride (III ), Boron chloride (III), boron bromide (III), boron halides such as boron (III); such as triphenylborane, tris (4-fluorophenyl) borane, tris (pentafluorophenyl) borane Triarylborane; tin halides such as tin (IV) fluoride, tin (IV) chloride, tin (IV) bromide, tin (IV) iodide; titanium fluoride (IV), titanium (IV) chloride, odor Titanium halides such as titanium (IV) iodide, titanium (IV) iodide; zinc fluoride (II), zinc chloride (II), zinc bromide II), zinc halides such as zinc iodide (II); selected from antimony halides such as antimony fluoride (V), antimony chloride (V), antimony bromide (V), antimony iodide (V), etc. A method for producing a silicon compound or a polymer thereof according to claim 12 (claim 13).

Furthermore, the present invention is the method for producing a silicon compound or a polymer thereof according to claim 13, wherein the Lewis acid catalyst is tris (pentafluorophenyl) borane (claim 14).

Next, the present invention is characterized in that the reaction solvent is selected from saturated aliphatic hydrocarbons having 6 to 10 carbon atoms, benzene, and aromatic hydrocarbons having 7 to 12 carbon atoms including a saturated alkyl group. A method for producing a silicon compound or a polymer thereof according to any one of claims 12 to 14 (claim 15).

In the present invention, a double-decker ring-closing T ₈ trans / cis isomer mixture is isolated by recrystallization, or a compound in which one isomer is excessive is provided, and a different polymerization utilizing the difference in geometric isomerism is used. It is intended to provide a polymer with high thermophysical properties.

It was clarified that the polymerization using these isomer non-equal mixtures showed a difference in the degree of polymerization reflecting geometric isomerism. In addition, it showed different properties such as thermal properties and film formability, and improved properties such as mechanical properties, thermal stability, and resistance.

For the polymerization, a Lewis acid such as tris (pentafluorophenyl) borane is used. It is known that when tris (pentafluorophenyl) borane is used, the stereochemistry of the silicon atom is retained. In addition, in the polymerization using tris (pentafluorophenyl) borane in an aromatic hydrocarbon solvent such as toluene or xylene, there is an advantage that the catalyst can be easily removed by a reprecipitation treatment after the reaction.

Hereinafter, the present invention will be described in more detail.

In the present invention, specifically, the general formula (1) or the general formula (2)

（式中、Ｒ，Ｘは前記の意味を表す）
で示される完全縮合オリゴシルセスキオキサンのトランス及び／又はシス立体異性体において、Ｘがイソブチル基である一般式（６）又は一般式（７）

(Wherein R and X represent the above meanings)
In the trans and / or cis stereoisomer of the fully condensed oligosilsesquioxane represented by the general formula (6) or the general formula (7), wherein X is an isobutyl group

（式中、Ｐｈはフェニル基を表す）
で代表される完全縮合オリゴシルセスキオキサンのトランス及び／又はシス立体異性体である。
本発明において、Ｘで表される炭素数４の飽和分枝状アルキル基の具体例としては、前記イソブチル基の他にｓｅｃ−ブチル基及びｔｅｒｔ−ブチル基が挙げられる。

(In the formula, Ph represents a phenyl group)
Is a trans and / or cis stereoisomer of a fully condensed oligosilsesquioxane represented by
In the present invention, specific examples of the saturated branched alkyl group having 4 carbon atoms represented by X include a sec-butyl group and a tert-butyl group in addition to the isobutyl group.

As described above, the present invention is characterized in that each isomer is separated from the trans / cis isomer mixture by recrystallization. Here, the solvent used in the recrystallization treatment is preferably a saturated aliphatic hydrocarbon having 6 to 10 carbon atoms, benzene, an aromatic hydrocarbon having 7 to 12 carbon atoms including a saturated alkyl group, or 1 carbon atom. Specific examples of the solvent selected from halogenated aliphatic hydrocarbons 1 to 3 and used for the recrystallization treatment include hexane, toluene, xylene, dichloromethane, and chloroform.

The temperature of the recrystallization treatment is preferably selected from temperatures between 30 ° C. and minus 80 ° C. Particularly preferably, it is 25 ° C. to −10 ° C.

Preferred examples of the recrystallization solvent include toluene and hexane as the recrystallization solvent used for the trans isomer separation of the general formula (6), the recrystallization temperature is around 0 ° C., and the general formula (7). As the recrystallization solvent used for the separation of cis-form, chloroform and hexane, the recrystallization temperature is around 25 ° C.

Next, the present invention relates to a trans and / or cis stereoisomer of the fully condensed oligosilsesquioxane represented by the general formula (6) or the general formula (7), for example, the general formula (8).

で示されるケイ素化合物を、ルイス酸触媒、反応溶媒の存在若しくは不存在下で反応させることを特徴とする一般式（９）又は一般式（１０）

The general formula (9) or the general formula (10) is characterized in that the silicon compound represented by the formula is reacted in the presence or absence of a Lewis acid catalyst and a reaction solvent.

（式中、Ｐｈはフェニル基を表す）
で示される構成単位からなるケイ素化合物又はその重合体の製造方法である。

(In the formula, Ph represents a phenyl group)
The manufacturing method of the silicon compound which consists of a structural unit shown, or its polymer.

As a preferred specific example of the polymer of the present invention, the repeating of the structural unit is 1 to 1000, and the more preferable repeating of the structural unit is 15 to 40.

In the production method using dehydrogenation coupling using a Lewis acid catalyst, the Lewis acid used is particularly preferably tris (pentafluorophenyl) borane.

Furthermore, in the method for producing a polymer, the reaction solvent is selected from saturated aliphatic hydrocarbons having 6 to 10 carbon atoms, benzene, and aromatic hydrocarbons having 7 to 12 carbon atoms including a saturated alkyl group. As the reaction solvent, toluene and xylene are used. A more preferred example is toluene.

In particular, polymerization using tris (pentafluorophenyl) borane in an aromatic hydrocarbon solvent such as toluene or xylene has an advantage that the catalyst can be easily removed by reprecipitation after the reaction.

Lewis acid catalyst amount used is 10 mol% from ^{10 -5} with respect to double-decker closed type _{T 8,} preferably in an amount of 1 mol% from 0.01.

The polymer comprising the T ₈ of the main chain of the structural units of the linear siloxanes, since the geometrical isomers of the monomers are reflected in the degree of polymerization of the polymer can be synthesized polymers even with the same molecular structure different molecular weights, which Thus, a new function can be imparted to the polymer so that the physical properties of the trans-form and cis-form of isoprene are different.
Further, by the polymer main chain is composed of linear siloxane T _8, since the Si-O composition ratio included in the main chain is high, excellent transparency, heat resistance, hardness, insulation, Oxygen plasma etching resistance and the like can be expected, and since it has an appropriate isopropyl group and other hydrocarbon substituents, solubility and film formability can also be imparted. Further, since T ₈ is included in the main chain as compared with ordinary polysiloxane, rigidity is also imparted.

The polymer obtained by the present invention is expected as a synthetic element for uses such as semiconductor encapsulants, various resists and pattern forming materials, oxygen absorbers and oxygen-absorbing resin compositions, and plasma display panels.

EXAMPLES Hereinafter, although a synthesis example and an Example demonstrate this invention further in detail, this invention is not restrict | limited at all by description of a following example. In the following synthesis examples and examples, Ph represents a phenyl group, iPr represents an isopropyl group, iBu represents an isobutyl group, and Et represents an ethyl group.

[Synthesis Example ^{_{1] T Ph 4 D Ph 4}} (ONa) 4 Synthesis of sodium hydroxide (6.4g, 0.16mol), isopropanol (240 mL), containing the ion-exchanged water (5.0 g, 0.28 mol) A 500 mL four-necked flask was purged with nitrogen. While stirring, phenyltrimethoxysilane (48.0 g, 0.24 mol) was added dropwise at room temperature over 15 minutes, followed by refluxing for 4 hours. After completion of the reaction, the mixture was allowed to cool to room temperature for 15 hours, and the precipitated solid was filtered, washed with isopropanol, and then dried under vacuum at 70 ° C. for 5 hours to obtain the desired product (23.9 g, 68% yield). .

Synthesis Example 2 Synthesis of T ^Ph ₈ ^DiBu ₂ (OH) ₂ T ^Ph ₄ D ^Ph ₄ (ONa) ₄ (3.00 g, 2.6 mmol), tetrahydrofuran (30 mL), triethylamine (0.78 g, 7. A 100 mL two-necked flask containing 7 mmol) was purged with nitrogen. While stirring, isobutyltrichlorosilane (1.5 g, 7.8 mmol) was added at room temperature and allowed to react for 12 hours at room temperature. Ion exchange water (13 mL) was added to the reaction mixture, and the mixture was stirred for 20 minutes. Toluene (70 mL) was added to remove the aqueous layer, followed by washing with ion-exchanged water. After anhydrous sodium sulfate was added for dehydration, the solution was concentrated and left at 0 ° C. overnight. Hexane was added to the precipitated crystals, and the mixture was further left at 0 ° C. overnight. The recrystallized product was filtered and dried to obtain the desired product (1.00 g, 30% yield).

Size exclusion chromatography (SEC), hydrogen nuclear magnetic resonance ( ¹ H-NMR; FIG. 1), silicon nuclear magnetic resonance ( ²⁹ Si-NMR), matrix-assisted laser desorption-type ionization-time-of-flight mass spectrometry ( The measurement results of MALDI-TOF-MS are shown below.

SEC: Mn = 1300, Mw / Mn = 1.0.
¹ H-NMR δ (CDCl ₃ , ppm): 0.80 (d, J = 7 Hz, 4H, trans form CH ₂ CH (CH ₃ ) ₂ ), 0.81 (d, J = 7 Hz, 4H, cis CH ₂ CH (CH ₃ ) ₂ ), 0.90 (d, J = 7 Hz, 12H, CH ₂ CH (CH ₃ ) ₂ ), 0.92 (d, J = 7 Hz, 12H, cis body of _{CH 2 CH (CH 3) 2} ), 1.81~2.00 (m, 4H, CH 2 CH (CH 3) 2), 2.59 (s, 4H, SiOH), 7.19~7 .57 (m, 80H, Ph).
²⁹ Si-NMR δ (CDCl ₃ , ppm): −79.33 (cis isomer), −79.29 (trans isomer), −79.20 (cis isomer), −78.91 (trans isomer and cis isomer) , -55.95 (trans and cis).
MALDI-TOF-MS (m / z): 1292.35 ([M + Na] ⁺ , calc. 1291.15).

[Example _^1] was added hexane to a toluene solution of _{^{T Ph 8 D iBu 2 (OH}} ) ₂ of the isomer separation trans / cis isomer mixtures ^{_{T Ph 8 D iBu 2 (OH}} ) 2 (1.00g), Left at 0 ° C. overnight. The precipitated crystals were filtered and separated into crystals (0.46 g, 92% recovery) and filtrate. The trans / cis isomer composition ratio of the obtained crystal was 8: 2. The crystals were recrystallized again to give only the trans isomer (0.36 g, 72% recovery).
Hexane was added to the concentrated chloroform solution of the filtrate and recrystallized at room temperature for 24 hours to obtain crystals having a trans / cis isomer composition ratio of 2: 8 (0.44 g, 88% recovery). Recrystallization again gave only the cis isomer (0.34 g, 68% recovery).

Trans body
¹ H-NMR δ (CDCl ₃ , ppm): 0.80 (d, J = 7 Hz, 4H, CH ₂ CH (CH ₃ ) ₂ ), 0.90 (d, J = 7 Hz, 12H, CH ₂ CH ( _{CH 3) 2), 1.81~2.00 (} m, 2H, CH 2 CH (CH 3) 2), 2.59 (s, 2H, SiOH), 7.19~7.57 (m, 40H , Ph).
²⁹ Si-NMR δ (CDCl ₃ , ppm): −79.30, −78.93, −55.96.

Cis body
¹ H-NMR δ (CDCl ₃ , ppm): 0.81 (d, J = 7 Hz, 4H, CH ₂ CH (CH ₃ ) ₂ ), 0.91 (d, J = 7 Hz, 12H, CH ₂ CH ( _{CH 3) 2), 1.81~2.00 (} m, 2H, CH 2 CH (CH 3) 2), 2.59 (s, 2H, SiOH), 7.19~7.57 (m, 40H , Ph).
²⁹ Si-NMR δ (CDCl ₃ , ppm): −79.34, −79.21, −78.91, −55.96.

Trans-isomer, cis-isomer, the respective ^{_{T Ph 8 D iBu 2 (OH}} ) 2 to ₂ ¹ H-NMR spectrum ((a) trans form, (b) cis ^form), FIG. 3 a 29 Si-NMR spectrum ( (A) trans isomer, (b) cis isomer).
The cis isomer crystal was further dissolved in chloroform / benzene (1: 2) and recrystallized to obtain a single crystal. The single crystal X-ray structure diffraction was measured to confirm the structure (FIG. 4). ).

Example 2 Dehydrogenation Polymerization Using Trans-T ^Ph ₈ ^DiBu ₂ (OH) _{2 In} a 30 mL two-necked flask substituted with argon, trans-T ^Ph ₈ ^DiBu ₂ (OH) ₂ obtained in Example 1 was used. Crystals (0.400 g, 0.31 mmol), dry toluene (2.5 mL), and tris (pentafluorophenyl) borane (3.3 mg, 2.1 mol%) were added. To this solution, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane (0.088 g, 0.31 mmol) was slowly added, followed by stirring at 60 ° C. for 12 hours. After adding methanol, the solvent was distilled off and dried to obtain polymer P1.

A ¹ H-NMR spectrum chart of the polymer P1 is shown in FIG.

Polymer P1
SEC: Mn = 39000, Mw / Mn = 1.6.
_{^{1 H-NMR δ (CDCl 3}} , ppm): - 0.11 (s, 12H, Si (CH 3) 2 O), - 0.03 (s, 12H, Si (CH 3) 2 O), 0. 71 (d, J = 7 Hz, 4H, CH ₂ CH (CH ₃ ) ₂ ), 0.87 (d, J = 7 Hz, 12H, CH ₂ CH (CH ₃ ) ₂ ), 1.75 to 1.99 ( _{m, 2H, CH 2 CH (} CH 3) 2), 7.11~7.55 (m, 40H, Ph).
²⁹ Si-NMR δ (CDCl ₃ , ppm): −79.68, −67.34, −21.25, −20.72.

Example 3 cis ^{_{-T Ph 8 D iBu 2 (OH}} ) cis obtained by dehydrogenation polymerization Example 1 using ^{_{2 -T Ph 8 D iBu 2 (}} OH) 2 crystals (0.400 g, 0.31 mmol ), The same experimental operation as in Example 2 was performed to obtain a polymer P2.
A ¹ H-NMR spectrum chart of the polymer P2 is shown in FIG.

Polymer P2
SEC: Mn = 29000, Mw / Mn = 1.7.
¹ H-NMR δ (CDCl ₃ , ppm): −0.06 (s, 12 H, Si (CH ₃ ) ₂ O), 0.02 (s, 12 H, Si (CH ₃ ) ₂ O), 0.78 (D, J = 7 Hz, 4H, CH ₂ CH (CH ₃ ) ₂ ), 0.94 (d, J = 7 Hz, 12H, CH ₂ CH (CH ₃ ) ₂ ), 1.84 to 2.03 (m _{, 2H, CH 2 CH (CH} 3) 2), 7.15~7.60 (m, 40H, Ph).
²⁹ Si-NMR δ (CDCl ₃ , ppm): −79.97, −79.70, −79.40, −67.31, −21.26, −20.69.

[Control Example 1] Dehydrogenation polymerization using T ^Ph ₈ D ^iBu ₂ (OH) ₂ in a trans / cis isomer mixture T ^Ph ₈ D ^iBu ₂ (OH) ₂ crystals (0.400 g) in a trans / cis isomer mixture , 0.31 mmol), and the same experimental operation as in Example 2 was performed to obtain a polymer P3.

Polymer P3
A ¹ H-NMR spectrum chart of the polymer P3 is shown in FIG.

SEC: Mn = 61000, Mw / Mn = 2.6.
¹ H-NMR δ (CDCl ₃ , ppm): −0.06 (s, 24H, Si (CH ₃ ) ₂ O), 0.03 (s, 24H, Si (CH ₃ ) ₂ O), 0.76 (D, J = 7 Hz, 4H, trans form CH ₂ CH (CH ₃ ) ₂ ), 0.77 (d, J = 7 Hz, 4H, cis form CH ₂ CH (CH ₃ ) ₂ ), 0.92 (D, J = 7 Hz, 12H, trans CH ₂ CH (CH ₃ ) ₂ ), 0.93 (d, J = 7 Hz, 12H, cis CH ₂ CH (CH ₃ ) ₂ ), 1.88 _{~2.04 (m, 4H, CH 2} CH (CH 3) 2), 7.12~7.56 (m, 80H, Ph).
²⁹ Si-NMR δ (CDCl ₃ , ppm): −79.91, −79.63, −79.36, −67.27, −21.18, −20.63.

[Example 4] Thermal analysis of polymer The thermophysical properties of the polymers obtained in Examples 2, 3 and 1 were examined using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). From the TGA measurement, the 5% weight loss temperature of polymer P1 in a nitrogen atmosphere is 495 ° C., the 5% weight loss temperature of polymer P2 is 494 ° C., and the 5% weight loss temperature of polymer P3 is 444 ° C. at 758 ° C. The residues were 79%, 77% and 71%, respectively (FIG. 6). From the DSC measurement, the glass transition temperature (Tg) of polymer P1 in a nitrogen atmosphere was 35 ° C., the glass transition temperature of polymer P2 was 30 ° C., and that of polymer P3 was 34 ° C.

T ₈ containing polymers with controlled these geometric isomers can be synthesized a clear polymer structure than ever. Use of these compounds is expected to show different properties in thermophysical properties, film formability, solvent resistance, film adhesion, oxygen plasma etching resistance, etc. when compared to polymers derived from trans / cis isomer mixtures. It is expected to be a synthetic element for applications such as various resists and pattern forming materials, oxygen absorbers and oxygen-absorbing resin compositions, and plasma display panels.

¹ H-NMR spectrum of T ^Ph ₈ ^DiBu ₂ (OH) ₂ of the trans / cis isomer mixture (A) ¹ H-NMR spectrum of T ^Ph ₈ ^DiBu ₂ (OH) ₂ in trans form, (b) cis form ²⁹ Si-NMR spectrum of ( ^Ph ₈ D ^iBu ₂ (OH) ₂ in (a) trans form, (b) cis form Single crystal X-ray structure diffraction of cis-T ^Ph ₈ ^DiBu ₂ (OH) ₂ (A) ¹ H-NMR spectrum of the polymer P1, (b) a polymer P2, (c) a polymer P3 TGA chart of (a) polymer P1, (b) polymer P2, (c) polymer P3

Claims (15)

General formula (1) or general formula (2)

(In the formula, each R is independently a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a cycloalkyl group. The alkyl group has 1 to 10 carbon atoms, and any hydrogen atom is a halogen atom or The aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, and the aryl group may have 6 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms. The arylalkyl group has 7 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms, and the cycloalkyl group has 3 to 10 carbon atoms. And any hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 10 carbon atoms, wherein X is It refers to a saturated branched alkyl group of prime 4.)
A trans and / or cis stereoisomer of a fully condensed oligosilsesquioxane represented by The trans and / or cis stereoisomer of the fully condensed oligosilsesquioxane according to claim 1, wherein R is a phenyl group in the general formula (1) or the general formula (2). The trans and / or cis stereoisomer of the fully condensed oligosilsesquioxane according to claim 1 or 2, wherein X in the general formula (1) or (2) is an isobutyl group. . General formula (1) and general formula (2)

(In the formula, each R is independently a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a cycloalkyl group. The alkyl group has 1 to 10 carbon atoms, and any hydrogen atom is a halogen atom or The aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, and the aryl group may have 6 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms. The arylalkyl group has 7 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms, and the cycloalkyl group has 3 to 10 carbon atoms. And any hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 10 carbon atoms, wherein X is It refers to a saturated branched alkyl group of prime 4.)
4. The trans and / or cis of the fully condensed oligosilsesquioxane according to claim 1, wherein each isomer is separated by recrystallization from a trans / cis isomer mixture represented by A method for producing a cis stereoisomer. The solvent for the recrystallization treatment is a saturated aliphatic hydrocarbon having 6 to 10 carbon atoms, benzene, an aromatic hydrocarbon having 7 to 12 carbon atoms including a saturated alkyl group, or a halogenated aliphatic hydrocarbon having 1 to 3 carbon atoms. The method for producing a trans and / or cis stereoisomer of the fully condensed oligosilsesquioxane according to claim 4, which is selected. The trans and / or cis stereoisomerism of the fully condensed oligosilsesquioxane according to any one of claims 4 to 5, wherein the temperature of the recrystallization treatment is selected from temperatures between 30 ° C and minus 80 ° C. Body manufacturing method. General formula (3) or general formula (4)

(In the formula, each R is independently a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a cycloalkyl group. The alkyl group has 1 to 10 carbon atoms, and any hydrogen atom is a halogen atom or The aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, and the aryl group may have 6 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms. The arylalkyl group has 7 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms, and the cycloalkyl group has 3 to 10 carbon atoms. And any hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 10 carbon atoms, and X is Saturated branched alkyl group of prime 4, n is an integer from 0 to 9, R ¹ is each independently an alkyl group. The number of carbon atoms in the alkyl group is from 1 to 10, any hydrogen atom (It may be substituted with a halogen atom or an alkyl group having 1 to 10 carbon atoms.)
A silicon compound or a polymer thereof comprising the structural unit represented by 8. The silicon compound or polymer thereof according to claim 7, wherein R in the general formula (3) or (4) is a phenyl group. The silicon compound or polymer thereof according to any one of claims 7 to 8, wherein in the general formula (3) or the general formula (4), X is an isobutyl group. The silicon compound or polymer thereof according to any one of claims 7 to 9, wherein, in the general formula (3) or the general formula (4), R ¹ is a methyl group. The silicon compound or polymer thereof according to any one of claims 7 to 10, wherein the repeating unit of the general formula (3) or the general formula (4) is 1 to 1000. General formula (1) or general formula (2)

(In the formula, each R is independently a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a cycloalkyl group. The alkyl group has 1 to 10 carbon atoms, and any hydrogen atom is a halogen atom or The aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, and the aryl group may have 6 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms. The arylalkyl group has 7 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms, and the cycloalkyl group has 3 to 10 carbon atoms. And any hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 10 carbon atoms, wherein X is It refers to a saturated branched alkyl group of prime 4.)
A trans and / or cis stereoisomer of a fully condensed oligosilsesquioxane represented by general formula (5):

(In the formula, n is an integer of 0 to 9, and R ¹ is each independently an alkyl group. The alkyl group has 1 to 10 carbon atoms, and any hydrogen atom is a halogen atom or 1 carbon atom. To 10 alkyl groups.)
The method for producing a silicon compound or a polymer thereof according to any one of claims 7 to 11, wherein the reaction is carried out in the presence or absence of a Lewis acid catalyst and a reaction solvent. . Lewis acid catalyst is an aluminum halide such as aluminum fluoride (III), aluminum chloride (III), aluminum bromide (III), aluminum iodide (III); boron fluoride (III), boron chloride (III), Boron halides such as boron bromide (III) and boron (III) iodide; triarylboranes such as triphenylborane, tris (4-fluorophenyl) borane and tris (pentafluorophenyl) borane; tin fluoride ( IV), tin halides such as tin chloride (IV), tin bromide (IV), tin (IV) iodide; titanium fluoride (IV), titanium chloride (IV), titanium bromide (IV), iodide Titanium halides such as titanium (IV); zinc fluoride (II), zinc chloride (II), zinc bromide (II), zinc iodide A zinc halide such as II); selected from antimony halides such as antimony fluoride (V), antimony chloride (V), antimony bromide (V), and antimony iodide (V). 12. A process for producing the silicon compound or polymer thereof according to 12. The method for producing a silicon compound or a polymer thereof according to claim 13, wherein the Lewis acid catalyst is tris (pentafluorophenyl) borane. The reaction solvent is selected from C6-C10 saturated aliphatic hydrocarbons, benzene, and C7-C12 aromatic hydrocarbons containing a saturated alkyl group. A method for producing a silicon compound or a polymer thereof according to claim 1.

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