JP2009263596A

JP2009263596A - Incompletely condensed oligosilsesquioxane and its production method

Info

Publication number: JP2009263596A
Application number: JP2008118084A
Authority: JP
Inventors: Yusuke Kawakami; 雄資川上; Fumio Oi; 册雄大井; Hiroyuki Yamamoto; 洋之山本; Goyuki Shinke; 悟之新家
Original assignee: Konishi Chemical Ind Co Ltd
Current assignee: Konishi Chemical Ind Co Ltd
Priority date: 2008-04-30
Filing date: 2008-04-30
Publication date: 2009-11-12

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new production method to obtain an incompletely condensed POSS derivative by rearranging the frame of a completely condensed POSS, and a new incompletely condensed POSS derivative obtained by the production method. <P>SOLUTION: Completely condensed octaphenyl octasilsesquioxane expressed by general formula (1) and completely condensed polyhedral origosilsesquioxane (POSS) expressed by general formula (2) are cohydrolyzed under existence of alkali in a water/alcohol solution, and if necessary, are then protected by a protecting group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、不完全縮合オリゴシルセスキオキサン及びその製造方法に関する。 The present invention relates to an incompletely condensed oligosilsesquioxane and a method for producing the same.

不完全縮合のオリゴシルセスキオキサン骨格は、シルセスキオキサンを含むポリマー、シリカ担持触媒、ネットワークポリマー等の合成ブロックとして重要な役割を果たしている（例えば、非特許文献１）。不完全縮合ポリヘドラルオリゴシルセスキオキサン（以下、ＰＯＳＳということがある）の合成について、Ｆｅｈｅｒらは完全縮合型ＰＯＳＳ骨格の「ｃｏｎｔｒｏｌｌｅｄｃｌｅａｖａｇｅ」を試みている（例えば、非特許文献２）。
マクロモレキュールス（Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ）２００７年,４０号,１６号,５６９８−５７０５頁ジャーナル・オブ・ディ・アメリカン・ケミカル・ソサエティ（Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．）１９９７年,１１９巻,４６号,１１３２３−１１３２４頁 The incompletely condensed oligosilsesquioxane skeleton plays an important role as a synthesis block for polymers containing silsesquioxane, silica-supported catalysts, network polymers and the like (for example, Non-Patent Document 1). Regarding the synthesis of incompletely condensed polyhedral oligosilsesquioxane (hereinafter sometimes referred to as POSS), Feher et al. Have attempted “controlled cleavage” of a fully condensed POSS skeleton (for example, Non-Patent Document 2).
Macromolecules 2007, No. 40, No. 16, pp. 5698-5705 Journal of the American Chemical Society (J. Am. Chem. Soc.) 1997, 119, 46, 11323-11324

本発明は、完全縮合型ＰＯＳＳの骨格の再配列により、不完全縮合ＰＯＳＳ誘導体を得る新規な製造方法の提供と、それによって得られた新規な不完全縮合ＰＯＳＳ誘導体の提供にある。 The present invention lies in the provision of a novel production method for obtaining an incompletely condensed POSS derivative by rearrangement of the skeleton of the fully condensed POSS and the provision of the novel incompletely condensed POSS derivative thus obtained.

本発明は、一般式（１）

The present invention relates to a general formula (1)

[式中、Ｐｈはフェニル基を表す。]
で示される完全縮合オクタフェニルオクタシルセスキオキサン（以下、Ｐｈ−Ｔ_８ということがある。）と、一般式（２） [Wherein Ph represents a phenyl group. ]
A fully condensed octaphenyl octasilsesquioxane (hereinafter sometimes referred to as Ph-T ₈ ) represented by formula (2)

[式中、Ｒは独立して水素原子、炭素数１〜１０のアルキル基、任意の水素原子が重水素、ハロゲン原子または炭素数１〜１０のアルキル基で置き換えられていてもよいアリール基、またはアリールにおける任意の水素がハロゲンまたは炭素数１〜１０のアルキル基で置き換えられていてもよいアリールアルキル基である。] [Wherein, R is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group in which any hydrogen atom may be replaced with deuterium, a halogen atom or an alkyl group having 1 to 10 carbon atoms, Or any hydrogen in aryl is an arylalkyl group which may be replaced by halogen or an alkyl group having 1 to 10 carbon atoms. ]

で示される完全縮合ポリヘドラルオリゴシルセスキオキサン（ＰＯＳＳ）を、水-アルコール溶媒中、アルカリの共存下、共加水分解反応させ、必要により、次いで保護基で保護することを特徴とする一般式（３） In general, the polycondensed oligosilsesquioxane (POSS) represented by the formula (1) is subjected to a cohydrolysis reaction in the presence of an alkali in a water-alcohol solvent, and then protected with a protecting group, if necessary. Formula (3)

[式中、Ｒ’はフェニル基と前記一般式（２）で示した置換基Ｒとのランダム混合物を表し、Ｒ’’はナトリウム（Ｎａ）又はＳｉ（Ｒ’’’）_３を表し、Ｒ’’’は水素原子、炭素数１から４の脂肪族炭化水素基又は更に置換基を有することもあるフェニル基を表す。] [Wherein R ′ represents a random mixture of a phenyl group and the substituent R shown in the general formula (2), R ″ represents sodium (Na) or Si (R ′ ″) ₃ , R "" Represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or a phenyl group which may further have a substituent. ]

で示される環状テトラシロキサン及び／又は一般式（４） And / or the general formula (4)

で示される環状ヘプタシルセスキオキサン及び／又は一般式（５） Cyclic heptasilsesquioxane and / or general formula (5)

で示される環状オクタシルセスキオキサンの製造方法である（請求項１）。 (Claim 1) It is a manufacturing method of cyclic octasilsesquioxane shown by these.

また、本発明は、アルコールが、炭素数１から４の分枝されていてもよい脂肪族アルコールから選択される請求項１に記載の製造方法である（請求項２）。 Moreover, this invention is a manufacturing method of Claim 1 as which alcohol is selected from the C1-C4 aliphatic alcohol which may be branched (Claim 2).

更に、本発明は、アルカリが、アルカリ金属水酸化物、アルカリ土類金属水酸化物、アルカリ金属炭酸塩、アルカリ土類金属炭酸塩、炭素数1から４のアルキル置換基をもつ四級アンモニウム塩の水酸化物及び炭素数１から４のアルキル置換基をもつ四級アンモニウム塩のフッ素物から選択される請求項１乃至請求項２の何れかに記載の製造方法である（請求項３）。 Furthermore, the present invention relates to a quaternary ammonium salt in which the alkali is an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal carbonate, an alkaline earth metal carbonate, or an alkyl substituent having 1 to 4 carbon atoms. The production method according to any one of claims 1 to 2, wherein the production method is selected from the hydroxides of quaternary ammonium salts having an alkyl substituent of 1 to 4 carbon atoms.

更にまた、本発明は、反応温度が、室温から溶媒の還流温度の範囲から選択される請求項１乃至請求項３の何れかに記載の製造方法である（請求項４）。
次に、本発明は、一般式（３） Furthermore, the present invention is the production method according to any one of claims 1 to 3, wherein the reaction temperature is selected from the range of room temperature to the reflux temperature of the solvent (claim 4).
Next, the present invention relates to a general formula (3)

[式中、Ｒ’はフェニル基と水素原子、炭素数１〜１０のアルキル基、任意の水素原子が重水素、ハロゲン原子または炭素数１〜１０のアルキル基で置き換えられていてもよいアリール基、またはアリールにおける任意の水素がハロゲンまたは炭素数１〜１０のアルキル基で置き換えられていてもよいアリールアルキル基とのランダム混合物を表し、Ｒ’’はナトリウム（Ｎａ）又はＳｉ（Ｒ’’’）_３を表し、Ｒ’’’は水素原子、炭素数１から４の脂肪族炭化水素基又は更に置換基を有することもあるフェニル基を表す。] [Wherein, R ′ represents a phenyl group and a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an arbitrary hydrogen atom optionally substituted with a deuterium atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms. Or any hydrogen in aryl represents a random mixture with halogen or an arylalkyl group optionally substituted with an alkyl group having 1 to 10 carbon atoms, and R ″ represents sodium (Na) or Si (R ′ ″) ₃ ) R ′ ″ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or a phenyl group which may further have a substituent. ]

で示される環状テトラシロキサンである（請求項５）。
また、本発明は、一般式（４） (Claim 5).
Further, the present invention provides a general formula (4)

で示される環状ヘプタシルセスキオキサンである（請求項６）。
更に、本発明は、一般式（５） (Claim 6).
Furthermore, the present invention relates to a general formula (5)

[式中、Ｒ’はフェニル基と水素原子、炭素数１〜１０のアルキル基、任意の水素原子が重水素、ハロゲン原子または炭素数１〜１０のアルキル基で置き換えられていてもよいアリール基、またはアリールにおける任意の水素がハロゲンまたは炭素数１〜１０のアルキル基で置き換えられていてもよいアリールアルキル基とのランダム混合物を表し、Ｒ’’はナトリウム（Ｎａ）又はＳｉ（Ｒ’’’）_３を表し、Ｒ’’’は水素原子、炭素数１から４の脂肪族炭化水素基又は更に置換基を有することもあるフェニル基を表す。]
で示される環状オクタシルセスキオキサンである（請求項７）。
また、本発明は、一般式（１）

[式中、Ｐｈはフェニル基を表す。]
で示される完全縮合オクタフェニルオクタシルセスキオキサン（Ｐｈ−Ｔ_８）と、一般式（６）

[式中、RはPh-d₅及び／又はo-MePhを表す。]
で示される完全縮合ポリヘドラルオリゴシルセスキオキサン（ＰＯＳＳ）を、水-アルコール溶媒中、アルカリの共存下、共加水分解反応させ、次いで保護基（クロロトリメチルシランなどのシランカップリング剤）で保護することを特徴とする一般式（７）

[式中、R’はフェニル（Ph）、Ph-d₅及び／又はo-MePhのランダム混合物を表す。]
で示される環状１，３，５，７−テトラキス（トリメチルシリル）テトラフェニルテトラシロキサン（Ｔ_４ＯＴＭＳ）及び／又は一般式（８）

[式中、R’はフェニル（Ph）、Ph-d₅及び／又はo-MePhのランダム混合物を表す。]
で示される環状３，７，１４−トリス（トリメチルシリル）ヘプタフェニルトリシクロ［７．３．３．１^５，１１］ヘプタシルセスキオキサン（Ｔ_７ＯＴＭＳ）及び／又は一般式（９）

[式中、R’はフェニル（Ph）、Ph-d₅及び／又はo-MePhのランダム混合物を表す。]
で示される環状５，１１，１４，１７−テトラキス（トリメチルシリル）オクタフェニルテトラシクロ［７．３．３．３^３，７］オクタシルセスキオキサン（ＤＤＴ_８ＯＴＭＳ）の製造方法である（請求項８）。
また、本発明は、一般式（７）

[式中、R’はフェニル（Ph）、Ph-d₅及び／又はo-MePhのランダム混合物を表す。]
で示される環状１，３，５，７−テトラキス（トリメチルシリル）テトラフェニルテトラシロキサン（Ｔ_４ＯＴＭＳ）である（請求項９）。
また、本発明は、一般式（８）

[式中、R’はフェニル（Ph）、Ph-d₅及び／又はo-MePhのランダム混合物を表す。]
で示される環状３，７，１４−トリス（トリメチルシリル）ヘプタフェニルトリシクロ［７．３．３．１^５，１１］ヘプタシルセスキオキサン（Ｔ_７ＯＴＭＳ）である（請求項１０）。
また、本発明は、一般式（９）

[式中、R’はフェニル（Ph）、Ph-d₅及び／又はo-MePhのランダム混合物を表す。]
で示される環状５，１１，１４，１７−テトラキス（トリメチルシリル）オクタフェニルテトラシクロ［７．３．３．３^３，７］オクタシルセスキオキサン（ＤＤＴ_８ＯＴＭＳ）である（請求項１１）。 [Wherein, R ′ represents a phenyl group and a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an arbitrary hydrogen atom optionally substituted with a deuterium atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms. Or any hydrogen in aryl represents a random mixture with halogen or an arylalkyl group optionally substituted with an alkyl group having 1 to 10 carbon atoms, and R ″ represents sodium (Na) or Si (R ′ ″) ₃ ) R ′ ″ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or a phenyl group which may further have a substituent. ]
The cyclic octasilsesquioxane represented by (7).
In addition, the present invention provides a general formula (1)

[Wherein Ph represents a phenyl group. ]
A fully condensed octaphenyl octasilsesquioxane (Ph-T ₈ ) represented by the general formula (6)

[Wherein, R represents Ph-d ₅ and / or o-MePh. ]
A fully condensed polyhedral oligosilsesquioxane (POSS) represented by the formula (1) is subjected to a co-hydrolysis reaction in the presence of an alkali in a water-alcohol solvent, followed by a protective group (a silane coupling agent such as chlorotrimethylsilane). General formula (7) characterized by protection

[Wherein R ′ represents a random mixture of phenyl (Ph), Ph-d ₅ and / or o-MePh. ]
Cyclic 1,3,5,7-tetrakis (trimethylsilyl) tetraphenyltetrasiloxane (T ₄ OTMS) and / or general formula (8)

[Wherein R ′ represents a random mixture of phenyl (Ph), Ph-d ₅ and / or o-MePh. ]
In shown are annular 3,7,14- tris (trimethylsilyl) heptaphenyl tricyclo ^{[7.3.3.1 5 and 11]} hept silsesquioxane _(T 7 OTMS) and / or formula (9)

[Wherein R ′ represents a random mixture of phenyl (Ph), Ph-d ₅ and / or o-MePh. ]
A cyclic 5,11,14,17-tetrakis (trimethylsilyl) octaphenyltetracyclo [7.3.3.3 ^3,7 ] octasilsesquioxane (DDT ₈ OTMS) represented by 8).
Further, the present invention provides a general formula (7)

[Wherein R ′ represents a random mixture of phenyl (Ph), Ph-d ₅ and / or o-MePh. ]
The cyclic 1,3,5,7-tetrakis (trimethylsilyl) tetraphenyltetrasiloxane (T ₄ OTMS) represented by (9).
Further, the present invention provides a compound represented by the general formula (8)

[Wherein R ′ represents a random mixture of phenyl (Ph), Ph-d ₅ and / or o-MePh. ]
Is in shown are annular 3,7,14- tris (trimethylsilyl) heptaphenyl tricyclo ^{[7.3.3.1 5 and 11]} hept silsesquioxane _(T 7 OTMS) (claim 10).
Further, the present invention provides a compound represented by the general formula (9)

[Wherein R ′ represents a random mixture of phenyl (Ph), Ph-d ₅ and / or o-MePh. ]
The cyclic 5,11,14,17-tetrakis (trimethylsilyl) octaphenyltetracyclo [7.3.3.3 ^3,7 ] octasil sesquioxane (DDT ₈ OTMS) represented by (11).

本発明は、完全縮合型ＰＯＳＳの骨格の再配列により、不完全縮合ＰＯＳＳ誘導体を得る新規な製造方法の提供と、それによって得られた新規な不完全縮合ＰＯＳＳ誘導体の提供にある。更に、これらのＰＯＳＳ誘導体は、各種レジスト及びパターン形成材料、酸素吸収剤及び酸素吸収樹脂組成物、プラズマディスプレイパネルなどの用途の資材として期待される。 The present invention lies in the provision of a novel production method for obtaining an incompletely condensed POSS derivative by rearrangement of the skeleton of the fully condensed POSS and the provision of the novel incompletely condensed POSS derivative thus obtained. Furthermore, these POSS derivatives are expected as materials for applications such as various resists and pattern forming materials, oxygen absorbents and oxygen-absorbing resin compositions, and plasma display panels.

本発明は、前述のとおり、一般式（１） As described above, the present invention relates to the general formula (1)

[式中、Ｐｈはフェニル基を表す。]
で示される完全縮合オクタフェニルオクタシルセスキオキサン（Ｐｈ−Ｔ_８）と、一般式（２） [Wherein Ph represents a phenyl group. ]
A fully condensed octaphenyl octasilsesquioxane (Ph-T ₈ ) represented by the general formula (2)

で示される環状オクタシルセスキオキサンの製造方法及び当該環状テトラシロキサン、ヘプタシルセスキオキサン及び環状オクタシルセスキオキサンである。
中でも、本発明は、一般式（１）

[式中、R’はフェニル（Ph）、Ph-d₅及び／又はo-MePhのランダム混合物を表す。]
で示される環状５，１１，１４，１７−テトラキス（トリメチルシリル）オクタフェニルテトラシクロ［７．３．３．３^３，７］オクタシルセスキオキサン（ＤＤＴ_８ＯＴＭＳ）の製造方法及び一般式（７）

[式中、R’はフェニル（Ph）、Ph-d₅及び／又はo-MePhのランダム混合物を表す。]
で示される環状１，３，５，７−テトラキス（トリメチルシリル）テトラフェニルテトラシロキサン（Ｔ_４ＯＴＭＳ）、一般式（８）

[式中、R’はフェニル（Ph）、Ph-d₅及び／又はo-MePhのランダム混合物を表す。]
で示される環状５，１１，１４，１７−テトラキス（トリメチルシリル）オクタフェニルテトラシクロ［７．３．３．３^３，７］オクタシルセスキオキサン（ＤＤＴ_８ＯＴＭＳ）である。 And the cyclic tetrasiloxane, heptasilsesquioxane and cyclic octasilsesquioxane.
Among these, the present invention provides the general formula (1)

[Wherein, R represents Ph-d ₅ and / or o-MePh. ]
A fully condensed polyhedral oligosilsesquioxane (POSS) represented by the formula (1) is subjected to a cohydrolysis reaction in the presence of an alkali in a water-alcohol solvent, and then with a protective group (a silane coupling agent such as chlorotrimethylsilane). General formula (7) characterized by protection

[Wherein R ′ represents a random mixture of phenyl (Ph), Ph-d ₅ and / or o-MePh. ]
A process for producing cyclic 5,11,14,17-tetrakis (trimethylsilyl) octaphenyltetracyclo [7.3.3.3 ^3,7 ] octasilsesquioxane (DDT ₈ OTMS) represented by formula (7) )

[Wherein R ′ represents a random mixture of phenyl (Ph), Ph-d ₅ and / or o-MePh. ]
Cyclic 1,3,5,7-tetrakis (trimethylsilyl) tetraphenyltetrasiloxane (T ₄ OTMS) represented by the general formula (8)

[Wherein R ′ represents a random mixture of phenyl (Ph), Ph-d ₅ and / or o-MePh. ]
Is in shown are annular 5,11,14,17- tetrakis (trimethylsilyl) octaphenyl tetracyclo [7.3.3.3 ^{3, 7]} octasilsesquioxane _(DDT 8 OTMS).

すなわち、本発明の共加水分解反応の反応機構は、Ｐｈ−Ｔ_８とオクタ（フェニル-ｄ_５）オクタシルセスキオキサン（Ｐｈ−ｄ_５−Ｔ_８）又はオクタ（o-メチルフェニル）オクタシルセスキオキサン（ｏ−ＭｅＰｈ−Ｔ_８）などとの共加水分解を行った（スキーム１参照）。 That is, the reaction mechanism of the co-hydrolysis reaction of the present invention, _{Ph-T 8} and octa (phenyl -d ₅₎ octasilsesquioxane _(Ph-d 5 -T ₈₎ or octa (o-methylphenyl) Okutashiru Cohydrolysis with sesquioxane (o-MePh-T ₈ ) or the like was performed (see Scheme 1).

スキーム１

Scheme 1

興味深いことに、この反応では置換基の置き換えが行われていることを発見した。以下の表1、Ｎｏ．１に示すように、Ｐｈ−Ｔ_８とＰｈ−ｄ_５−Ｔ_８の共加水分解を行うと、ＤＤＴ_８ＯＴＭＳだけでなくＴ_７ＯＴＭＳも生成した。 Interestingly, we found that this reaction involves substitution of substituents. The following Table 1, No. As shown in 1, when the co-hydrolysis of _{Ph-T 8} and _Ph-d 5 -T _{_8,} was also generated _T 7 OTMS well DDT 8 OTMS.

ａ；（Ｐｈ−Ｔ_８＋Ｐｈ−ｄ_５−Ｔ_８）／溶媒＝１ｍｍｏｌ／２５ｍＬ
ｂ；（Ｐｈ−Ｔ_８＋ｏ−ＭｅＰｈ−Ｔ_８）／溶媒＝１ｍｍｏｌ／９ｍＬ
ｃ：（Ｐｈ−Ｔ_８＋Ｐｈ−ｄ_５−Ｔ_８）／溶媒＝１ｍｍｏｌ／２２ｍＬ
還流温度：オイルバス下約９０℃ _{a; (Ph-T 8 +} Ph-d 5 -T 8) / solvent = 1 mmol / 25 mL
b; (Ph-T ₈ + o-MePh-T ₈ ) / solvent = 1 mmol / 9 mL
_{c: (Ph-T 8 +} Ph-d 5 -T 8) / solvent = 1 mmol / 22 mL
Reflux temperature: about 90 ° C under oil bath

ＤＤＴ_８ＯＴＭＳとＴ_７ＯＴＭＳのモル比は^２９Ｓｉ−ＮＭＲから、約１．５／１であった。カラムクロマトグラフィー精製後の重量比は、２．３３／１となった。同じ条件下で、Ｐｈ−Ｔ_８とオクタ（ｏ-メチルフェニル）オクタシルセスキオキサン（ｏ−ＭｅＰｈ−Ｔ_８）の共加水分解では、Ｔ_７ＯＴＭＳのみが生成した（表1、Ｎｏ．２）。完全縮合型ＰＯＳＳの加水分解では、置換基の立体的大きさが影響していることが考えられる。 The molar ratio of DDT ₈ OTMS and T ₇ OTMS was about 1.5 / 1 from ²⁹ Si-NMR. The weight ratio after purification by column chromatography was 2.33 / 1. Under the same conditions, co-hydrolysis of Ph-T ₈ and octa (o-methylphenyl) octasilsesquioxane (o-MePh-T ₈ ) produced only T ₇ OTMS (Table 1, No. 2). ). In the hydrolysis of the fully condensed POSS, it is considered that the steric size of the substituent influences.

両Ｔ_７ＯＴＭＳとＤＤＴ_８ＯＴＭＳのシルセスキオキサン骨格の^２９Ｓｉ−ＮＭＲピークは２つの異なる化学シフトとして観察される。この理由として、フェニル基とフェニル-ｄ_５基が、Ｔ_７やダブルデッカー（ＤＤＴ_８）骨格中にランダムに分布しているためと考えられる。より定量的なデータはマトリックス支援レーザー脱離方式イオン化-飛行時間型質量分析装置（ＭＡＬＤＩ−ＴＯＦ−ＭＳ）から得ている。重水素化した置換基は、両Ｔ_７ＯＴＭＳとＤＤＴ_８ＯＴＭＳにランダムに分布していた（表２）。 The ²⁹ Si-NMR peaks of the silsesquioxane skeleton of both T ₇ OTMS and DDT ₈ OTMS are observed as two different chemical shifts. This is probably because the phenyl group and the phenyl-d ₅ group are randomly distributed in T ₇ and the double-decker (DDT ₈ ) skeleton. More quantitative data is obtained from a matrix-assisted laser desorption ionization-time-of-flight mass spectrometer (MALDI-TOF-MS). The deuterated substituents were randomly distributed in both T ₇ OTMS and DDT ₈ OTMS (Table 2).

類似現象として、Ｐｈ−Ｔ_８とｏ−ＭｅＰｈ−Ｔ_８の共加水分解でも見られた。生成したＴ_７ＯＴＭＳの複雑な^２９Ｓｉ−ＮＭＲは、Ｔ_７ＯＴＭＳのフェニル基とｏ-メチルフェニル基がランダムに分布していることを示唆している。ＭＡＬＤＩ−ＴＯＦ−ＭＳの測定結果は、それぞれ異なるフェニル/ｏ-メチルフェニル比をもつＴ_７ＯＴＭＳがあることを示している（表２）。Ｔ_７ＯＴＭＳにおいて、フェニル基とｏ-メチルフェニル基が統計学的にランダムに分布していることがわかる。 As a similar phenomenon was also observed in the co-hydrolysis of the _{Ph-T 8} and the _{o-MePh-T 8.} The complex ²⁹ Si-NMR of the generated T ₇ OTMS suggests that the phenyl groups and o-methylphenyl groups of T ₇ OTMS are randomly distributed. The MALDI-TOF-MS measurement results show that there are T ₇ OTMSs with different phenyl / o-methylphenyl ratios (Table 2). It can be seen that in T ₇ OTMS, phenyl groups and o-methylphenyl groups are statistically randomly distributed.

表２に示すように、溶媒の還流温度でＤＤＴ_８ＯＴＭＳとＴ_７ＯＴＭＳの置換基の置き換えがおこっているが、Ｔ_４ＯＴＭＳでは室温でおこっている。
実験事実に基づき、反応機構を上記、スキーム１のように考えた。 As shown in Table 2, substitution of DDT ₈ OTMS and T ₇ OTMS substituents occurs at the reflux temperature of the solvent, whereas T ₄ OTMS occurs at room temperature.
Based on the experimental facts, the reaction mechanism was considered as shown in Scheme 1 above.

Ｔ_８が単純に加水分解しているなら、Ｔ_７ＯＴＭＳとＤＤＴ_８ＯＴＭＳの骨格に結合している置換基は、一種類と考えられるが（スキーム１上段）、これは正しくない。Ｐｈ−Ｔ_８とＰｈ−ｄ_５−Ｔ_８、もしくはｏ−ＭｅＰｈ−Ｔ_８の共加水分解では、生成物中にランダムに置換基が分布していることから、「再配列（ｒｅｓｈｕｆｆｌｉｎｇｐｒｏｃｅｓｓ）」でＰＯＳＳが加水分解している大きな証拠である。すなわち、完全縮合型ＰＯＳＳが分解して小さなフラグメントになり、再組み立てによりＤＤＴ_８やＴ_７構造になるということである。 If T ₈ is simply hydrolyzed, the substituents attached to the skeletons of T ₇ OTMS and DDT ₈ OTMS are considered to be one type (Scheme 1 top), which is incorrect. In the co-hydrolysis of Ph-T ₈ and Ph-d ₅ -T ₈ , or o-MePh-T ₈ , since the substituents are randomly distributed in the product, the “reshuffling process” This is great evidence that POSS is hydrolyzed. That is, the fully condensed POSS is decomposed into small fragments and reassembled into a DDT ₈ or T ₇ structure.

つまり、選択的な反応条件下では、完全縮合型ＰＯＳＳの加水分解により生じた不完全縮合のオリゴシルセスキオキサン骨格は、制御された構造の環状四量体、Ｔ_７、そしてＤＤＴ_８に再構築される。加水分解反応は、「再配列」である。 That is, under selective reaction conditions, the incompletely condensed oligosilsesquioxane skeleton generated by hydrolysis of the fully condensed POSS is reconstituted into a controlled structure of the tetramer, T ₇ , and DDT ₈ . Built. The hydrolysis reaction is “rearrangement”.

以下、本発明の加水分解反応の実際について更に具体的に説明する。
本発明の製造方法に用いられる炭素数１から４の分枝されていてもよい脂肪族アルコールとしては、具体的には、エタノール、２−プロパノール、２-メチル−１−プロパノール、ｎ−ブタノールもしくはＳｅｃ−ブタノールなどが挙げられる。中でも、２−プロパノールもしくは２-メチル−１−プロパノールが好ましくは用いられる。 Hereinafter, the actual hydrolysis reaction of the present invention will be described more specifically.
Specific examples of the aliphatic alcohol having 1 to 4 carbon atoms which may be used in the production method of the present invention include ethanol, 2-propanol, 2-methyl-1-propanol, n-butanol or Examples include Sec-butanol. Of these, 2-propanol or 2-methyl-1-propanol is preferably used.

本発明の製造方法に用いられるアルカリとしては、アルカリ金属水酸化物、アルカリ土類金属水酸化物、アルカリ金属炭酸塩、アルカリ土類金属炭酸塩、炭素数1から４のアルキル置換基をもつ四級アンモニウム塩の水酸化物、炭素数１から４のアルキル置換基をもつ四級アンモニウム塩のフッ素物から選択されるが、具体的には、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウムなどが挙げられる。中でも、水酸化ナトリウムが好ましくは用いられる。 Examples of the alkali used in the production method of the present invention include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, and four alkyl substituents having 1 to 4 carbon atoms. Selected from hydroxides of quaternary ammonium salts and fluorides of quaternary ammonium salts having an alkyl substituent of 1 to 4 carbon atoms, specifically, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate Etc. Of these, sodium hydroxide is preferably used.

本発明の製造方法において、加水分解反応の反応温度は、室温から水−アルコール溶媒の還流温度の範囲内で選択される。 In the production method of the present invention, the reaction temperature of the hydrolysis reaction is selected within the range of room temperature to the reflux temperature of the water-alcohol solvent.

本発明の製造方法において、原料・反応試剤の仕込みモル比は、Ｐｈ−Ｔ_８: Ｐｈ―ｄ_５又はｏ−ＭｅＰｈ−Ｔ_８：Ｈ_２Ｏ：ＮａＯＨが１：１：４：８を中心とした任意の範囲から適宜、選択される。 In the production method of the present invention, the charged molar ratio of the raw material and the reaction reagent is mainly about Ph-T ₈ : Ph-d ₅ or o-MePh-T ₈ : H ₂ O: NaOH 1: 1: 4: 8. It is suitably selected from the arbitrary range.

本発明の製造方法において、目的物の取出し、分離方法は、晶析法又は濃縮乾固法による通常の方法によって行われる。 In the production method of the present invention, the object is taken out and separated by an ordinary method such as a crystallization method or a concentration to dryness method.

以下、実施例によって本発明の方法を更に具体的に説明する。 Hereinafter, the method of the present invention will be described more specifically with reference to examples.

実施例１
Ｐｈ−ｄ_５−Ｔ_８（０．１１ｇ，０．１０ｍｍｏｌ）、Ｐｈ−Ｔ_８（０．１１ｇ，０．１０ｍｍｏｌ）、水酸化ナトリウム（０．０３３ｇ，０．８２ｍｍｏｌ）、水（０．００７３ｇ，０．４１ｍｍｏｌ）及び２−プロパノール（５ｍＬ）を反応器に加え、窒素置換したのち、還流下で２４時間攪拌した。反応終了後、ろ過により白色固体を得、２−プロパノールで洗浄して、真空下、７０℃で乾燥させ、白色固体（０．１５ｇ）を得た。生成物を同定しやすくするために、ＯＮａ基を以下の実験手順でトリメチルシリル（ＴＭＳ）基保護した。３０ｍＬの二口フラスコに上記生成物を加えて置換した。氷水浴下、テトラヒドロフラン（ＴＨＦ）、トリエチルアミン（１．８ｇ，１７．８ｍｍｏｌ）、クロロトリメチルシランを反応器に加え、反応溶液を室温下で3時間攪拌し、氷水浴下で水を反応器にゆっくり加えた。攪拌を止めて有機層を分離し、蒸留水を加えて洗浄して中性にし、ヘキサンを有機層に加えた。Ｔ_７ＯＴＭＳとＤＤＴ_８ＯＴＭＳはカラムクロマトグラフィー（４５−７５μｍのシリカゲルで、四塩化炭素を使用）で分離することができる［薄層クロマトグラフィー（ＴＬＣ）：Ｒｆ_{ＤＤＴ８ＯＴＭ}Ｓ＝０．６０; Ｒｆ_{Ｔ７ＯＴＭＳ}＝０．４４］。ＤＤＴ_８ＯＴＭＳ/ Ｔ_７ＯＴＭＳの重量比は、２．３３／１であった。 Example 1
Ph-d ₅ -T ₈ (0.11 g, 0.10 mmol), Ph-T ₈ (0.11 g, 0.10 mmol), sodium hydroxide (0.033 g, 0.82 mmol), water (0.0073 g, 0.41 mmol) and 2-propanol (5 mL) were added to the reactor, purged with nitrogen, and then stirred under reflux for 24 hours. After completion of the reaction, a white solid was obtained by filtration, washed with 2-propanol, and dried at 70 ° C. under vacuum to obtain a white solid (0.15 g). To facilitate product identification, the ONa group was protected with a trimethylsilyl (TMS) group by the following experimental procedure. The above product was added to and replaced in a 30 mL two-necked flask. Tetrahydrofuran (THF), triethylamine (1.8 g, 17.8 mmol) and chlorotrimethylsilane were added to the reactor in an ice water bath, the reaction solution was stirred at room temperature for 3 hours, and water was slowly added to the reactor in an ice water bath. added. Stirring was stopped and the organic layer was separated, washed with distilled water to neutralize, and hexane was added to the organic layer. T ₇ OTMS and DDT ₈ OTMS can be separated by column chromatography (45-75 μm silica gel using carbon tetrachloride) [thin layer chromatography (TLC): Rf _DDT8OTMS S = 0.60; Rf _T7OTMS = 0.44]. The weight ratio of DDT ₈ OTMS / T ₇ OTMS was 2.33 / 1.

ＳＥＣ：Ｍｗ／Ｍｎ＝１２５０／１２４０．
ＭＡＬＤＩ−ＴＯＦ−ＭＳ：図１、図２（Ｔ_７ＯＴＭＳの部分拡大図）及び図３（ＤＤＴ_８ＯＴＭＳの部分拡大図）
^２９Ｓｉ−ＮＭＲ δ (ｐｐｍ):１１．５４ (ＯＳｉＭｅ_３ｉｎＴ_７ＯＴＭＳ);１０．５１ (Ｏ_３ＳｉＰｈｉｎＤＤＴ_８ＯＴＭＳ);−７６．０２, −７８．８５ (Ｏ_３ＳｉＰｈ−ｄ_５ｉｎＤＤＴ_８ＯＴＭＳ);−７６．１２， −７８．９４ (Ｏ_３ＳｉＰｈｉｎＤＤＴ_８ＯＴＭＳ);−７７．３３,−７７．９１,−７８．１９ (Ｏ_３ＳｉＰｈ−ｄ_５ｉｎＴ_７ＯＴＭＳ);−７７．４２,−７７．９９,−７８．２６ (Ｏ_３ＳｉＰｈｉｎＴ_７ＯＴＭＳ部分拡大図)（図４）． SEC: Mw / Mn = 1250/1240.
MALDI-TOF-MS: FIG. 1, FIG. 2 (partially enlarged view of T ₇ OTMS) and FIG. 3 (partially enlarged view of DDT ₈ OTMS)
²⁹ Si-NMR δ (ppm): 11.54 (OSiMe ₃ in T ₇ OTMS); 10.51 (O ₃ SiPh in DDT ₈ OTMS); −76.02, −78.85 (O ₃ SiPh-d ₅ in DDT ₈ OTMS); −76.12, −78.94 (O ₃ SiPh in DDT ₈ OTMS); −77.33, −77.91, −78.19 (O ₃ SiPh-d ₅ in T ₇ OTMS) ); -77.42, -77.99, -78.26 (O ₃ SiPh in T ₇ OTMS partially enlarged view) (FIG. 4).

実施例２
ｏ−ＭｅＰｈ−Ｔ_８（０．３１ｇ，０．２７ｍｍｏｌ）、Ｐｈ−Ｔ_８（０．２８ｇ，０．２７ｍｍｏｌ）、水酸化ナトリウム（０．０８６ｇ，２．２ｍｍｏｌ）、水（０．０１９ｇ，１．１ｍｍｏｌ）、２−プロパノール（５ｍＬ）を用い、実験操作は還流下、実施例１の加水分解と同様の方法で行い、白色固体（０．２７ｇ）を得た。 Example 2
o-MePh-T ₈ (0.31 g, 0.27 mmol), Ph-T ₈ (0.28 g, 0.27 mmol), sodium hydroxide (0.086 g, 2.2 mmol), water (0.019 g, 1 0.1 mmol) and 2-propanol (5 mL), and the experimental operation was performed in the same manner as the hydrolysis in Example 1 under reflux to obtain a white solid (0.27 g).

ＳＥＣ：Ｍｗ／Ｍｎ＝１１６０／１１５５．
ＭＡＬＤＩ−ＴＯＦ−ＭＳ（図５）．
^２９Ｓｉ−ＮＭＲ δ (ｐｐｍ): １０．４９〜１１．３７ (ｍ，ＯＳｉＭｅ_３); −７８．８８〜−７６．８３ (ｍ，Ｏ_３ＳｉＰｈ) （図６）.
SEC: Mw / Mn = 1160/1155.
MALDI-TOF-MS (FIG. 5).
²⁹ Si-NMR δ (ppm): 10.49 to 11.37 (m, OSiMe ₃ ); −78.88 to −76.83 (m, O ₃ SiPh) (FIG. 6).

実施例３
Ｐｈ−Ｔ_８（０．０９６３ｇ，０．０９３ｍｍｏｌ）、Ｐｈ−ｄ_５−Ｔ_８（０．１０００ｇ，０．０９３ｍｍｏｌ）、水酸化ナトリウム（０．０３０ｇ，７５ｍｍｏｌ）の入っている５０ｍＬ二口フラスコを同様に窒素置換した。２−プロパノール（４ｍＬ）と水（０．００６７ｇ，０．３７ｍｍｏｌ）を反応器に加え、室温下で４０時間攪拌した。反応終了後、ろ過により白色固体を得、２−プロパノールで洗浄して、真空下、７０℃で５時間乾燥させた。収量：０．０５８３ｇ。生成物をトリメチルシリル基で保護し、同様の手順で還流下、Ｐｈ−Ｔ_８の加水分解生成物を処理した。白色固体と、粘性の無色透明液体を得た。収量：０．０２７８ｇ。ＭＡＬＤＩ−ＴＯＦ−ＭＳによる生成物の同定を図７に示す。
Example 3
A 50 mL two-necked flask containing Ph-T ₈ (0.0963 g, 0.093 mmol), Ph-d ₅ -T ₈ (0.1000 g, 0.093 mmol), and sodium hydroxide (0.030 g, 75 mmol) was added. Similarly, nitrogen substitution was performed. 2-Propanol (4 mL) and water (0.0067 g, 0.37 mmol) were added to the reactor and stirred at room temperature for 40 hours. After completion of the reaction, a white solid was obtained by filtration, washed with 2-propanol, and dried under vacuum at 70 ° C. for 5 hours. Yield: 0.0583g. The product was protected with a trimethylsilyl group and the Ph-T ₈ hydrolysis product was treated under reflux in the same procedure. A white solid and a viscous colorless transparent liquid were obtained. Yield: 0.0278 g. The product identification by MALDI-TOF-MS is shown in FIG.

これらのＰＯＳＳは、各種レジスト及びパターン形成材料、酸素吸収剤及び酸素吸収樹脂組成物、プラズマディスプレイパネルなどの用途の合成素子として期待される。 These POSSs are expected as synthetic elements for applications such as various resists and pattern forming materials, oxygen absorbers and oxygen-absorbing resin compositions, and plasma display panels.

トリメチルシリル基保護したＰｈ−Ｔ_８とＰｈ−ｄ_５−Ｔ_８を還流下、共加水分解して得られた生成物のＭＡＬＤＩ−ＴＯＦ−ＭＳを示す。 ₃ shows MALDI-TOF-MS of a product obtained by cohydrolyzing Ph-T ₈ and Ph-d ₅ -T ₈ protected with trimethylsilyl group under reflux. トリメチルシリル基保護したＰｈ−Ｔ_８とＰｈ−ｄ_５−Ｔ_８を還流下、共加水分解して得られた生成物のＭＡＬＤＩ−ＴＯＦ−ＭＳ（Ｔ_７ＯＴＭＳの部分拡大図を示す。Reflux _{Ph-T 8} and _Ph-d 5 -T ₈ that trimethylsilyl groups protected, shows a partial enlarged view of the _{MALDI-TOF-MS (T 7} OTMS co hydrolyzing the resulting product. トリメチルシリル基保護したＰｈ−Ｔ_８とＰｈ−ｄ_５−Ｔ_８を還流下、共加水分解して得られた生成物のＭＡＬＤＩ−ＴＯＦ−ＭＳ（ＤＤＴ_８ＯＴＭＳの部分拡大図）を示す。The MALDI-TOF-MS (partially enlarged view of DDT ₈ OTMS) of the product obtained by cohydrolyzing Ph-T ₈ and Ph-d ₅ -T ₈ protected with trimethylsilyl group under reflux is shown. トリメチルシリル基保護したＰｈ−Ｔ_８とＰｈ−ｄ_５−Ｔ_８を還流下、共加水分解して得られた生成物の^２９Ｓｉ−ＮＭＲを示す。The ²⁹ Si-NMR of the product obtained by cohydrolyzing Ph-T ₈ and Ph-d ₅ -T ₈ protected with trimethylsilyl group under reflux is shown. トリメチルシリル基保護したＰｈ−Ｔ_８とｏ−ＭｅＰｈ−Ｔ_８を室温下、共加水分解して得られた生成物のＭＡＬＤＩ−ＴＯＦ−ＭＳを示す。At room temperature and _{Ph-T 8} and _{o-MePh-T 8} was trimethylsilyl group protected shows, MALDI-TOF-MS, of co-hydrolyzing the resulting product. トリメチルシリル基保護したＰｈ−Ｔ_８とｏ−ＭｅＰｈ−Ｔ_８を還流下、共加水分解して得られた生成物の^２９Ｓｉ−ＮＭＲを示す。The ²⁹ Si-NMR of the product obtained by cohydrolyzing Ph-T ₈ and o-MePh-T ₈ protected with trimethylsilyl group under reflux is shown. トリメチルシリル基保護したＰｈ−Ｔ_８とＰｈ−ｄ_５−Ｔ_８を還流下、共加水分解して得られた生成物の^２９Ｓｉ−ＮＭＲを示す。The ²⁹ Si-NMR of the product obtained by cohydrolyzing Ph-T ₈ and Ph-d ₅ -T ₈ protected with trimethylsilyl group under reflux is shown.

Claims

General formula (1)

[Wherein Ph represents a phenyl group. ]
A fully condensed octaphenyl octasilsesquioxane (Ph-T ₈ ) represented by the general formula (2)

[Wherein, R is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group in which any hydrogen atom may be replaced with deuterium, a halogen atom or an alkyl group having 1 to 10 carbon atoms, Or any hydrogen in aryl is an arylalkyl group which may be replaced by halogen or an alkyl group having 1 to 10 carbon atoms. ]
A general condensed polyhedral oligosilsesquioxane (POSS) represented by the following general co-hydrolysis reaction in the presence of an alkali in a water-alcohol solvent, and then protected with a protecting group, if necessary: Formula (3)

[Wherein R ′ represents a random mixture of a phenyl group and the substituent R shown in the general formula (2), R ″ represents sodium (Na) or Si (R ′ ″) ₃ , R "" Represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or a phenyl group which may further have a substituent. ]
And / or the general formula (4)

[Wherein R ′ represents a random mixture of a phenyl group and the substituent R shown in the general formula (2), R ″ represents sodium (Na) or Si (R ′ ″) ₃ , R "" Represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or a phenyl group which may further have a substituent. ]
Cyclic heptasilsesquioxane and / or general formula (5)

[Wherein R ′ represents a random mixture of a phenyl group and the substituent R shown in the general formula (2), R ″ represents sodium (Na) or Si (R ′ ″) ₃ , R "" Represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or a phenyl group which may further have a substituent. ]
The manufacturing method of cyclic octasilsesquioxane shown by these.

The production method according to claim 1, wherein the alcohol is selected from aliphatic alcohols having 1 to 4 carbon atoms which may be branched.

Alkali is alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, alkaline earth metal carbonate, quaternary ammonium salt hydroxide and carbon having an alkyl substituent of 1 to 4 carbon atoms and carbon The production method according to any one of claims 1 to 2, wherein the production method is selected from fluorides of quaternary ammonium salts having an alkyl substituent of 1 to 4.

The production method according to any one of claims 1 to 3, wherein the reaction temperature is selected from the range of room temperature to the reflux temperature of the solvent.

General formula (3)

[Wherein, R ′ is independently a phenyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an arbitrary hydrogen atom substituted with a deuterium atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms. A good aryl group, or a random mixture of any hydrogen in the aryl with a halogen or an arylalkyl group optionally substituted with an alkyl group having 1 to 10 carbon atoms, wherein R ″ is sodium (Na) or Si (R ''') ₃ and R''' represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or a phenyl group which may further have a substituent. ]
A cyclic tetrasiloxane represented by

General formula (4)

[Wherein, R ′ is independently a phenyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an arbitrary hydrogen atom substituted with a deuterium atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms. A good aryl group, or a random mixture of any hydrogen in the aryl with a halogen or an arylalkyl group optionally substituted with an alkyl group having 1 to 10 carbon atoms, wherein R ″ is sodium (Na) or Si (R ''') ₃ and R''' represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or a phenyl group which may further have a substituent. ]
Cyclic heptasilsesquioxane represented by

General formula (5)

[Wherein, R ′ is independently a phenyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an arbitrary hydrogen atom substituted with a deuterium atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms. A good aryl group, or a random mixture of any hydrogen in the aryl with a halogen or an arylalkyl group optionally substituted with an alkyl group having 1 to 10 carbon atoms, wherein R ″ is sodium (Na) or Si (R ''') ₃ and R''' represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or a phenyl group which may further have a substituent. ]
A cyclic octasilsesquioxane represented by

General formula (1)

[Wherein R ′ represents a random mixture of phenyl (Ph), Ph-d ₅ and / or o-MePh. ]
Method for producing in shown are annular 5,11,14,17- tetrakis (trimethylsilyl) octaphenyl tetracyclo [7.3.3.3 ^{3, 7]} octasilsesquioxane _(DDT 8 OTMS).

General formula (7)

[Wherein R ′ represents a random mixture of phenyl (Ph), Ph-d ₅ and / or o-MePh. ]
A cyclic 1,3,5,7-tetrakis (trimethylsilyl) tetraphenyltetrasiloxane (T ₄ OTMS) represented by:

General formula (8)

[Wherein R ′ represents a random mixture of phenyl (Ph), Ph-d ₅ and / or o-MePh. ]
In shown are annular 3,7,14- tris (trimethylsilyl) heptaphenyl tricyclo ^{[7.3.3.1 5 and 11]} hept silsesquioxane _(T 7 OTMS).

General formula (9)

[Wherein R ′ represents a random mixture of phenyl (Ph), Ph-d ₅ and / or o-MePh. ]
Cyclic 5,11,14,17-tetrakis (trimethylsilyl) octaphenyltetracyclo [7.3.3.3 ^3,7 ] octasilsesquioxane (DDT ₈ OTMS).