JP4655790B2 - Silicon compounds - Google Patents

Description

  The present invention relates to a novel silicon compound that can effectively impart the characteristics of a fluorine-containing organic group to various solids. “Silsesquioxane” is a class name indicating a compound in which each silicon atom is bonded to three oxygen atoms, and each oxygen atom is bonded to two silicon atoms. “Silsesquioxane” is sometimes used as a general term for a silsesquioxane structure and a silsesquioxane-like structure in which a part thereof is deformed.

  Until now, from the viewpoint of high-performance coating on solid surfaces, Teflon (registered trademark) and other fluorine-containing organic groups introduce fluorine-specific properties (water repellency, oil repellency, chemical resistance, Attempts to impart slipperiness, difficulty adhesion, and wear resistance have been widely made and put into practical use. In particular, various silane coupling agents have been developed to improve adhesion and adhesion to a solid surface, and fluorine-containing silane coupling agents are used. The fluorine-containing silane coupling agent is designed such that a fluorine-containing organic group in the molecule is responsible for imparting properties, and another functional group in the same molecule reacts with a hydroxyl group on the solid surface.

  However, since the functional group responsible for adhesion to the solid is an alkoxy group or a silanol group in an aqueous solution, a uniform fluorine-containing organic group coating is effectively applied on the solid surface by reaction between coupling agents. However, there is a need for a technique for imparting the characteristics of a fluorine-containing organic group more effectively.

  On the other hand, many studies have been conducted on silsesquioxane so far. For example, Non-Patent Document 1 does not show a certain structure in addition to a ladder structure, a fully condensed structure, and an incompletely condensed structure. The presence of silsesquioxane such as an amorphous structure is described.

  Among silsesquioxanes, those having a fully condensed structure that forms a closed space can hold a plurality of organic groups in the molecule. In this respect, by introducing a plurality of functional functional groups into a fully condensed silsesquioxane, it becomes possible to concentrate functional functional groups with the silsesquioxane skeleton as the core. It is expected that the characteristics of the functional functional group can be effectively expressed.

However, silsesquioxane having a fully condensed structure having a plurality of fluorine-containing organic groups and high reaction activity on the solid surface has not been synthesized so far. Synthesis of silsesquioxane having reactive activity is desired.
Chem. Rev. 95, 1409 (1995)

  An object of the present invention is to provide a novel feature of having a plurality of fluorine-containing organic groups and having high reaction activity in order to effectively impart the characteristics of fluorine-containing organic groups to various solids. It is to provide a silicon compound.

In order to effectively impart the characteristics of a fluorine-containing organic group, the present inventors have paid attention to a fully condensed silsesquioxane capable of holding a plurality of organic groups in the molecule. At the same time, attention was focused on halogenated silanes from the viewpoint of reaction activity on various solids. As used with silylating agents, halogenated silanes can replace active groups in organic substances such as hydroxyl groups, amino groups, carboxyl groups, amide groups, and mercapto groups with silicon. Halogenated silanes have high activity and versatility. For example, to other active silane compounds such as alkoxysilanes, acyloxysilanes, silthians, (iso) cyansilanes, isocyanatosilanes, isothiocyanatosilanes and aminosilanes. Can be induced to a wide range of other chemical species. Therefore, a fully condensed structure silsesquioxane derivative having a highly reactive fluorine-containing organic group was found by incorporating a silyl halide group into the silsesquioxane skeleton. That is, the present invention has the following configuration.

ここに、Ａは下記式（２）で示される基であり；Ｒ¹は炭素数１〜４０のアルキル、アリールおよびアリールアルキルから独立して選択される基であって、いずれも、その少なくとも１つの水素がフッ素で置き換えられた基であり；この炭素数１〜４０のアルキルにおいて、任意の−ＣＨ₂−は−Ｏ−、シクロアルキレンまたはフェニレンで置き換えられてもよく；このアリールアルキルにおいて、任意の−ＣＨ₂−は−Ｏ−、シクロアルキレンまたはフェニレンで置き換えられてもよい。

ここに、Ｚ ¹ は炭素数２〜１０のアルキレンであって、このアルキレンにおける任意の−ＣＨ ₂ −は−Ｏ−またはフェニレンで置き換えられてもよく；Ｒ ² は炭素数１〜２０のアルキル、炭素数６〜２０のアリールまたは炭素数７〜２０のアリールアルキルであり；Ｘ ¹ はハロゲンであり；そして、ｎは０〜２の整数である。
[1] Silicon compound represented by formula (1):

Here, A is a group represented by the following formula (2) ; R ¹ is a group independently selected from alkyl, aryl and arylalkyl having 1 to 40 carbon atoms, each of which is at least 1 A group in which one hydrogen is replaced by fluorine; in the alkyl having 1 to 40 carbon atoms, any —CH ₂ — may be replaced by —O—, cycloalkylene or phenylene; in this arylalkyl, —CH ₂ — may be replaced by —O—, cycloalkylene or phenylene.

Here, Z ¹ is alkylene having 2 to 10 carbons, and any —CH ₂ — in the alkylene may be replaced by —O— or phenylene; R ² is alkyl having 1 to 20 carbons ; C 6-20 aryl or C 7-20 arylalkyl; X ¹ is halogen; and n is an integer of 0-2.

[ 2 ] The compound according to [1], wherein R ¹ in the formula (1) according to [1] is fluoroalkyl having 1 to 20 carbon atoms.

[ 3 ] R ¹ in the formula (1) described in [1] is 2-fluoroethyl, 2,2-difluoroethyl, 3,3,3-trifluoropropyl, nonafluoro-1,1,2,2-tetrahydro Hexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H-dodecyl or perfluoro-1H, The compound according to [1], which is 1H, 2H, 2H-tetradecyl.

[ 4 ] R ¹ in the formula (1) according to [1] is 3,3,3-trifluoropropyl, nonafluoro-1,1,2,2-tetrahydrohexyl or tridecafluoro-1,1,2, The compound according to [1], which is 2-tetrahydrooctyl.

[ 5 ] The compound according to [1], wherein R ¹ in Formula (1) according to [1] is 3,3,3-trifluoropropyl or nonafluoro-1,1,2,2-tetrahydrohexyl.

[ 6 ] The compound according to [1], wherein Z ¹ is alkylene having 2 to 8 carbon atoms; and n is 0 or 1.

[7] Z ¹ is an alkylene of 2 to 4 carbon atoms; and n is 0 or 1, compounds described in [1].

[8] ^[1] R 1 in the formula (1) according to the be 3,3,3-trifluoropropyl; Z ¹ in the formula (2) is alkylene of 2 or 3 carbon atoms; and n is The compound according to [1] , which is 0.

ここに、Ｒ¹は炭素数１〜４０のアルキル、アリールおよびアリールアルキルから独立して選択される基であって、いずれも、その少なくとも１つの水素がフッ素で置き換えられた基であり；この炭素数１〜４０のアルキルにおいて、任意の−ＣＨ₂−は−Ｏ−、シクロアルキレンまたはフェニレンで置き換えられてもよく；このアリールアルキルにおいて、任意の−ＣＨ₂−は−Ｏ−、シクロアルキレンまたはフェニレンで置き換えられてもよく；Ｚ³は単結合または炭素数１〜８のアルキレンであり、そしてこのアルキレンにおける任意の−ＣＨ₂−は−Ｏ−またはフェニレンで置き換えられてもよく；Ｒ²は炭素数１〜２０のアルキル、炭素数６〜２０のアリールまたは炭素数７〜２０のアリールアルキルであり；Ｘ¹はハロゲンであり；そして、ｎは０〜２の整数である。
[ 9 ] A method for producing a silicon compound represented by formula (1-1), wherein step (b) is carried out following step (a1):

Wherein R ¹ is a group independently selected from alkyl having 1 to 40 carbons, aryl and arylalkyl, each of which is a group in which at least one hydrogen is replaced by fluorine; In the alkyl group of 1 to 40, any —CH ₂ — may be replaced by —O—, cycloalkylene, or phenylene; in this arylalkyl, any —CH ₂ — represents —O—, cycloalkylene, or phenylene. Z ³ is a single bond or alkylene having 1 to 8 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O— or phenylene; R ² is carbon C 1 -C 20 alkyl, aryl alkyl aryl or 7 to 20 carbon atoms having 6 to 20 carbon atoms; X ¹ is halogen And, n represents an integer of 0 to 2.

ここに、Ｍは１価のアルカリ金属原子であり；Ｘ²はハロゲンであり；そして、Ｒ¹およびＺ³は、式（１−１）におけるＲ¹およびＺ³とそれぞれ同一の意味を有する。 <Step (a1)>
A step of obtaining a compound represented by the formula (6) by reacting a compound represented by the formula (3) with a compound represented by the formula (5):

Here, M is a monovalent alkali metal atom; X ² is halogen; and R ¹ and Z ³ have the same meaning as R ¹ and Z ³ in formula (1-1), respectively.

ここに、Ｒ²およびＸ¹は式（１−１）におけるＲ²およびＸ¹とそれぞれ同一の意味を有する。 <Step (b)>
A step of obtaining a compound represented by the formula (1-1) by reacting a compound represented by the formula (6) with a compound represented by the formula (7) in the presence of a transition metal catalyst:

Here, R ² and X ¹ have the respective same meaning as R ² and X ¹ in formula (1-1).

ここに、Ｒ¹は炭素数１〜４０のアルキル、アリールおよびアリールアルキルから独立して選択される基であって、いずれも、その少なくとも１つの水素がフッ素で置き換えられた基であり；この炭素数１〜４０のアルキルにおいて、任意の−ＣＨ₂−は−Ｏ−、シクロアルキレンまたはフェニレンで置き換えられてもよく；このアリールアルキルにおいて、任意の−ＣＨ₂−は−Ｏ−、シクロアルキレンまたはフェニレンで置き換えられてもよく；Ｚ³は単結合または炭素数１〜８のアルキレンであり、そしてこのアルキレンにおける任意の−ＣＨ₂−は−Ｏ−またはフェニレンで置き換えられてもよく；Ｒ²は炭素数１〜２０のアルキル、炭素数６〜２０のアリールまたは炭素数７〜２０のアリールアルキルであり；Ｘ¹はハロゲンであり；そして、ｎは０〜２の整数である。
[ 10 ] A method for producing a silicon compound represented by formula (1-1), wherein step (b) is carried out following step (a2):

Wherein R ¹ is a group independently selected from alkyl having 1 to 40 carbons, aryl and arylalkyl, each of which is a group in which at least one hydrogen is replaced by fluorine; In the alkyl group of 1 to 40, any —CH ₂ — may be replaced by —O—, cycloalkylene, or phenylene; in this arylalkyl, any —CH ₂ — represents —O—, cycloalkylene, or phenylene. Z ³ is a single bond or alkylene having 1 to 8 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O— or phenylene; R ² is carbon C 1 -C 20 alkyl, aryl alkyl aryl or 7 to 20 carbon atoms having 6 to 20 carbon atoms; X ¹ is halogen And, n represents an integer of 0 to 2.

ここに、Ｘ²はハロゲンであり；そして、Ｒ¹およびＺ³は式（１−１）におけるＲ¹およびＺ³とそれぞれ同一の意味を有する。 <Step (a2)>
A step of obtaining a compound represented by the formula (6) by reacting a compound represented by the formula (4) with a compound represented by the formula (5):

Where X ² is halogen; and R ¹ and Z ³ have the same meaning as R ¹ and Z ³ in formula (1-1), respectively.

ここに、Ｒ²およびＸ¹は式（１−１）におけるＲ²およびＸ¹とそれぞれ同一の意味を有する。 <Step (b)>
A step of obtaining a compound represented by the formula (1-1) by reacting a compound represented by the formula (6) with a compound represented by the formula (7) in the presence of a transition metal catalyst:

Here, R ² and X ¹ have the respective same meaning as R ² and X ¹ in formula (1-1).

[ 11 ] In the formula (1-1), R ¹ is 2-fluoroethyl, 2,2-difluoroethyl, 3,3,3-trifluoropropyl, nonafluoro-1,1,2,2-tetrahydrohexyl, trideca Fluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H-dodecyl or perfluoro-1H, 1H, 2H, The production method according to [ 9 ] or [ 10 ], which is 2H-tetradecyl.

[ 12 ] In formula (1-1), R ¹ is 3,3,3-trifluoropropyl or nonafluoro-1,1,2,2-tetrahydrohexyl; and n is 0 or 1;
[ 9 ] or the production method according to [ 10 ].

[ 13 ] A silane coupling agent comprising the silicon compound according to any one of [1] to [ 8 ].

[ 14 ] A solid surface treating agent comprising the silicon compound according to any one of [1] to [ 8 ].

  The silicon compound provided by the present invention is a silsesquioxane derivative having a fluorine-containing organic group that exhibits water repellency and oil repellency, and has excellent reactivity. The silicon compound of the present invention has a plurality of fluorine-containing organic groups and has a halogenated silyl group having high reaction activity, so that various compounds have characteristics (water repellent, oil repellent, It is possible to effectively impart chemical resistance, slipperiness, hard adhesion, and abrasion resistance). In addition, it can be expanded to various chemical species by functional group conversion of halogenated silyl groups.

  First, terms used in the present invention will be described. In the present invention, both alkyl and alkylene may be a linear group or a branched group. Both cycloalkyl and cycloalkylene may or may not be a bridged ring structure group. “Arbitrary” used in the present invention indicates that not only the position but also the number can be arbitrarily selected. And the expression “any A may be replaced by B or C” means that at least one A is replaced by B and at least one A is replaced by C, at least one It is meant to include the case where A is replaced by B and at least one other A is replaced by C. A compound represented by the formula (1) may be referred to as a compound (1). The compounds represented by other formulas may be represented by the same simplification method.

式（１）におけるＲ¹は炭素数１〜４０のアルキル、アリールおよびアリールアルキルから独立して選択される基であって、いずれも、その少なくとも１つの水素がフッ素で置き換えられている基である。この炭素数１〜４０のアルキルおよびアリールアルキル中のアルキレンにおいて、任意の−ＣＨ₂−は−Ｏ−、シクロアルキレンまたはフェニレンで置き換えられてもよい。 The silicon compound of the present invention is represented by the formula (1).

R ¹ in the formula (1) is a group independently selected from alkyl having 1 to 40 carbon atoms, aryl and arylalkyl, each of which is a group in which at least one hydrogen is replaced by fluorine. . In the alkylene in the alkyl and arylalkyl having 1 to 40 carbon atoms, arbitrary —CH ₂ — may be replaced by —O—, cycloalkylene or phenylene.

When R ¹ is alkyl in which at least one hydrogen is replaced by fluorine, the carbon number is 1-40. The number of preferable carbons is 1-20, and the more preferable number of carbons is 1-14.

Examples of alkyl having 1 to 14 carbon atoms and wherein at least one hydrogen is replaced by fluorine are 2-fluoroethyl, 2,2-difluoroethyl, 3,3,3-trifluoropropyl, nonafluoro- 1,1,2,2-tetrahydrohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H-dodecyl and perfluoro-1H, 1H, 2H, 2H-tetradecyl.

When R ¹ is aryl in which at least one hydrogen is replaced by fluorine, the preferred carbon number is 6-10. Aryl may have a substituent other than fluorine.

  Examples of aryl in which at least one hydrogen is replaced by fluorine are pentafluorophenyl, 4-fluorophenyl, 2,3-difluoro-4-methylphenyl, 2,3-difluoro-4-methoxyphenyl, 2,3- Difluoro-4-ethoxyphenyl, 2,3-difluoro-4-propoxyphenyl and 2,3,5,6-tetrafluoro-4-vinylphenyl.

When R ¹ is arylalkyl in which at least one hydrogen is replaced by fluorine, its preferred carbon number is 7-12, and any —CH ₂ — in this group is —O—, cycloalkylene or phenylene. It may be replaced.

  Examples of arylalkyl in which at least one hydrogen is replaced by fluorine are 4-fluorophenylmethyl, 2,3,4,5,6-pentafluorophenylmethyl, 2- (2,3,4,5,6 -Pentafluorophenyl) ethyl, 3- (2,3,4,5,6-pentafluorophenyl) propyl, 2- (2-fluorophenyl) propyl and 2- (4-fluorophenyl) propyl.

Particularly preferred examples of R ¹ are 3,3,3-trifluoropropyl, nonafluoro-1,1,2,2-tetrahydrohexyl and tridecafluoro-1,1,2,2-tetrahydrooctyl.

A in the formula (1) is a group having a halogenated silyl group, and a preferred example thereof is a group represented by the formula (2).

In the formula (2), R ² is an arylalkyl of 7-20 aryl or a carbon number of 6 to 20 alkyl, the number of carbon atoms of 1 to 20 carbon atoms. Preferred examples of R ² are alkyl having 1 to 8 carbon atoms and aryl having 6 to 12 carbon atoms, and more preferred examples are alkyl having 1 to 4 carbon atoms. Z ¹ is alkylene having 2 to 10 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O— or phenylene. X ¹ is halogen. Preferred examples of X ¹ are chlorine and bromine, and the most preferred example is chlorine. N is an integer of 0 to 2, preferably 0 or 1.

式（２−１）において、Ｚ³は単結合または炭素数１〜８のアルキレンである。そしてこのアルキレンにおいて、任意の−ＣＨ₂−は−Ｏ−またはフェニレンで置き換えられてもよい。式（２−１）におけるＲ²、Ｘ¹およびｎは、式（２）におけるＲ²、Ｘ¹およびｎとそれぞれ同一の意味を有する。 In introducing an organic group onto a Si atom, a method for obtaining a derivative that does not undergo hydrolysis includes a method in which a Grignard reagent is reacted with Si-halogen and a compound having an aliphatic unsaturated bond with respect to Si-H. There is a method of reacting. The latter is usually referred to as a hydrosilylation reaction method. In the present invention, it is advantageous to employ a hydrosilylation reaction method in the preparation of the compound (1). That is, a compound having an Si—H functional group is bonded to a silsesquioxane having an organic group having an unsaturated bond at the terminal by a hydrosilylation reaction. Therefore, Z ¹ is preferably a group represented by —Z ³ —C ₂ H ₄ —. That is, a preferred example of the formula (2) is a group represented by the formula (2-1).

In Formula (2-1), Z ³ is a single bond or alkylene having 1 to 8 carbon atoms. In this alkylene, arbitrary —CH ₂ — may be replaced by —O— or phenylene. R ^2, X ¹ and n in the formula (2-1) have respective same meaning as R ^2, X ¹ and n in Formula (2).

That is, preferred examples of Z ¹ _{is, -C 2 H 4 -, -} C 3 H 6 -, - C 4 H 8 -, - C 5 H 10 -, - C 6 H 12 -, - C 8 H 16, —C ₂ H ₄ —O—C ₂ H ₄ — and —C ₃ H ₆ —O—C ₃ H ₆ —, and more preferred examples are —C ₂ H ₄ — and —C ₃ H ₆ —. However, the selection range of Z ¹ is not limited to these.

  The silicon compound of the present invention has a halogenated silyl group. The halogenated silyl group has a high reaction activity, and can be derived into alkoxylane by reacting with alcohol, metal alcoholate, ethylene oxide, or orthoformate, acid anhydride, sodium acylate In addition, it is possible to induce aminosilane or silazane by reacting ammonia, primary and secondary amines with acyloxysilane by reacting with an organic acid. Examples of species that can be similarly derived are silthian, isocyanatosilane, and isothiocyanatosilane. By performing functional group conversion in this way, it is possible to control the reactivity and ease of handling of the silicon compound of the present invention.

  The application range of silyl halide groups is diversified by substitution reaction with active hydrogen in organic compounds. Examples of groups having active hydrogen are hydroxyl, amino, carboxyl, amide and mercapto groups. For this reason, it is possible to bind the silicon compound of the present invention to an organic compound having these groups, and it is useful as a modifier for the physical properties of the target organic compound.

  The silyl halide group of the silicon compound of the present invention has high hydrolyzability, and acts as a silane coupling agent that easily forms a good bond with an inorganic compound by hydrolysis or the like. Therefore, coating on a solid surface including a glass substrate is possible, and it is useful as a raw material for a composite material composed of an organic compound and an inorganic compound.

The silicon compound of the present invention is used as a silane coupling agent for surface treatment of inorganic fine particles, metallic silicon (such as silicon wafers), mica, stainless steel, aluminum, ceramics, cement, paper, glass, plastic, inorganic ceramic substrates, and fabrics. It is possible to use. Examples of the inorganic fine _{particles, SiO 2, Al 2 O 3} , MgO, MgCl 2, ZrO 2, TiO 2, B 2 O 3, CaO, ZnO, BaO, V 2 O 5, Cr 2 O 3, and be ThO Or a mixture containing these. Complex oxides of these atoms such as SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ — MgO or the like may be used. Further, known magnetic materials, for example, metals such as iron, cobalt and nickel and alloys thereof, metal oxides such as Fe ₃ O ₄ , γ-Fe ₂ O ₃ and cobalt-added iron oxide, Mn · Zn ferrite, Ni · Ferrite such as Zn ferrite, magnetite, and hematite can also be used as inorganic fine particles. In addition, the object which uses the silicon compound of this invention as a silane coupling agent is not limited to these examples.

スキーム１および２において、Ｍ²は水素原子または１価のアルカリ金属原子であり、その他の記号の意味は前記の通りである。 Next, the manufacturing method of a compound (1-1) among the silicon compounds of this invention is demonstrated. Preferred examples of the production method of compound (1-1) are shown in Schemes 1 and 2. In the scheme, compounds having a terminal unsaturated bond are exemplified, but the present invention is not limited thereto.

In Schemes 1 and 2, M ² is a hydrogen atom or a monovalent alkali metal atom, and the meanings of other symbols are as described above.

化合物（４）は、トリクロロシラン誘導体を加水分解し、さらに熟成させることにより合成することができる。例えば、Frank J. Feherらは、シクロペンチルトリクロロシランを水−アセトン混合溶剤中で、室温下または還流温度下で反応させ、さらに２週間熟成させることにより、式（４）においてＲ¹がシクロペンチルである化合物を得ている（Organometallics, 10,2526-(1991)、Chemical European Journal, 3,No.6,900-(1997)）。本発明においては含フッ素有機基を有するトリクロロシラン誘導体を用いることにより、同様にＲ¹が含フッ素有機基である化合物（４）を得ることができる。 In scheme 1, a preferred raw material is compound (4).

Compound (4) can be synthesized by hydrolyzing a trichlorosilane derivative and further aging. For example, Frank J. Feher et al. Reacted cyclopentyltrichlorosilane in a water-acetone mixed solvent at room temperature or reflux temperature, and further aged for 2 weeks, whereby R ¹ is cyclopentyl in formula (4). The compound has been obtained (Organometallics, 10,2526- (1991), Chemical European Journal, 3, No. 6,900- (1997)). In the present invention, by using a trichlorosilane derivative having a fluorine-containing organic group, a compound (4) in which R ¹ is a fluorine-containing organic group can be obtained.

式（３）中のＭは１価のアルカリ金属原子である。そして、アルカリ金属の好ましい例はナトリウムおよびカリウムであり、特に好ましい例はナトリウムである。化合物（３）は、３個の加水分解性基を有するシラン化合物を加水分解することにより得られるシルセスキオキサンオリゴマーを、有機溶剤中で１価のアルカリ金属水酸化物と反応させることにより得られる。３個の加水分解性基を有するシラン化合物を、有機溶剤、水およびアルカリ金属水酸化物の存在下で、加水分解、縮合させることによっても得られる。いずれの方法の場合も、短時間、且つ高収率で化合物（３）を製造することができる（国際公開パンフレットＷＯ０２／０９４８３９を参照）。化合物（３）は、化合物（４）のシラノール基よりも高い反応性を示す。従って、この化合物（３）を原料として用いれば、容易かつ高収率でその誘導体を合成することができる。即ち、本発明の原料としては、化合物（４）よりも化合物（３）の方が好ましい。 Another preferred raw material used in Scheme 1 is a silsesquioxane compound represented by the formula (3).

M in Formula (3) is a monovalent alkali metal atom. Preferred examples of the alkali metal are sodium and potassium, and a particularly preferred example is sodium. Compound (3) is obtained by reacting a silsesquioxane oligomer obtained by hydrolyzing a silane compound having three hydrolyzable groups with a monovalent alkali metal hydroxide in an organic solvent. It is done. It can also be obtained by hydrolyzing and condensing a silane compound having three hydrolyzable groups in the presence of an organic solvent, water and an alkali metal hydroxide. In any case, the compound (3) can be produced in a short time and with a high yield (see International Publication Pamphlet WO02 / 094839). Compound (3) exhibits a higher reactivity than the silanol group of compound (4). Therefore, if this compound (3) is used as a raw material, its derivative can be synthesized easily and with high yield. That is, as the raw material of the present invention, the compound (3) is preferable to the compound (4).

The production method of the compound (1-3) in which Z ¹ is —C ₃ H ₆ — and n is 0 will be described in detail. However, the compound of the present invention is not limited to this.

式（５−３）においてＸ²はハロゲンであり、好ましくは塩素または臭素である。

According to scheme 1, compound (3) or (4) is reacted with trihalogenated silane compound (5-3) having an aliphatic unsaturated bond to give compound (6-3).

In the formula (5-3), X ² is halogen, preferably chlorine or bromine.

  In order to synthesize the compound (6-3) from the compound (4) and the compound (5-3), a method called “Corner-capping reaction” can be employed. This is a reaction using so-called nucleophilic substitution, and is described in, for example, Macromolecules, 28, 8435- (1995). The conditions for selecting the solvent used in this nucleophilic substitution reaction are that it does not react with the compound (4) and the compound (5-3) and that it is sufficiently dehydrated. Examples of solvents are tetrahydrofuran, toluene, methylene chloride and dimethylformamide. Particularly preferred solvents are well dehydrated methylene chloride or tetrahydrofuran. A preferred amount of compound (5-3) to be used is 1 to 5 times in terms of molar ratio to compound (4). Since hydrogen chloride is generated during this reaction, it is necessary to remove this hydrogen chloride from the reaction system. Although there is no restriction | limiting in the method of removing hydrogen chloride, It is preferable to use various organic bases. Examples of the organic base include pyridine, dimethylaniline, triethylamine, and tetramethylurea. However, the organic base is not limited to these compounds as long as the side reaction can be suppressed and the intended reaction can proceed promptly. A particularly preferred example of the organic base is triethylamine. The preferable usage-amount of a triethylamine is 3-15 times in the molar ratio with respect to a compound (4). The reaction temperature is a temperature at which a side reaction does not occur simultaneously and a quantitative nucleophilic substitution reaction can proceed. However, when charging the raw materials, it is most preferable to carry out under low temperature conditions, for example, in an ice bath, and thereafter at room temperature. The reaction time is not particularly limited as long as it is sufficient for the quantitative nucleophilic substitution reaction to proceed, and the compound (6-3) can be usually obtained in 4 hours.

  The reaction of compound (3) with compound (5-3) to give compound (6-3) can also be carried out in the same manner as in the case of using compound (4). The preferable usage-amount of a compound (5-3) is 1-5 times in the molar ratio with respect to a compound (3). In this reaction, it is not necessary to use an organic base or the like for the purpose of removing hydrogen chloride. However, an organic base may be used as a catalytic role for promptly proceeding the reaction. The organic base is not particularly limited as long as the side reaction can be suppressed and the target reaction can proceed promptly. Examples of organic bases are pyridine, dimethylaniline, triethylamine and tetramethylurea. A more preferred example of the organic base is triethylamine. When using triethylamine, it is preferable that it is 1-5 times by the equivalent ratio with respect to Si-ONa in a compound (3). The solvent used in the reaction, the reaction temperature, and the reaction time are the same as in the reaction using the compound (4).

When a distillation method is applied to remove unreacted raw material compounds and solvents (hereinafter sometimes referred to as “impurities”), the target compound is retained by being kept under high temperature conditions for a long time. There is a risk of disassembly. Therefore, in order to remove impurities efficiently without impairing the purity of the compound (6-3), it is preferable to use a purification method by recrystallization operation or an impurity extraction method with an organic solvent. The purification method by recrystallization is performed as follows. First, compound (6-
The mixture of 3) and impurities is dissolved in a solvent that dissolves them together. The preferable density | concentration of the compound (6-3) at this time is 1 to 15 weight%. Next, the solution is concentrated by a concentrating device such as a rotary evaporator under reduced pressure until crystals begin to precipitate. Thereafter, the pressure is returned to atmospheric pressure and kept at room temperature or low temperature. Thereafter, the solvent containing impurities and the precipitated solid component can be separated by filtration or centrifugation. Of course, since the target compound is also contained in the solvent containing impurities, it is possible to increase the recovery rate of the compound (6-3) by repeating the above operation.

  The preferred solvent selection conditions for recrystallization are that it does not react with the compound (6-3), that the compound (6-3) and impurities are dissolved in the stage before concentration, and that only the impurities are dissolved in the compound ( 6-3) is efficiently precipitated, and has a relatively low boiling point. Examples of preferred solvents that satisfy such conditions are esters and aromatics. Particularly preferred solvents are ethyl acetate and toluene. And in order to raise a refinement | purification further, what is necessary is just to increase the repetition frequency of recrystallization operation.

  The extraction method of impurities with an organic solvent is performed as follows. First, a mixture of the compound (6-3) and impurities is dispersed in an organic solvent that dissolves only the impurities, and only the impurities are extracted while stirring. Thereafter, the solid-liquid is separated by filtration or centrifugation to obtain the compound (6-3). There is no particular limitation as long as it is an organic solvent that does not dissolve the compound (6-3) and dissolves only impurities, but alcohols such as methanol, ethanol and isopropyl alcohol, and aromatic hydrocarbons such as toluene and xylene are preferred. . The extraction time is not particularly limited as long as impurities can be efficiently removed, but is preferably in the range of 1 to 5 hours. The extraction temperature is not particularly limited as long as impurities can be efficiently removed, but is preferably in the range of 10 to 150 ° C, more preferably 10 to 50 ° C, and most preferably 10 to 40 ° C. And in order to raise a refinement | purification further, what is necessary is just to increase the frequency | count of repetition of extraction operation of the impurity by an organic solvent.

式（７−３）におけるＸ¹の意味は前記の通りであり、塩素が最も好ましい。 The compound (1-3) is obtained by subjecting the compound (6-3) obtained in Scheme 1 and the following compound (7-3) to a hydrosilylation reaction in the presence of a transition metal catalyst.

The meaning of X ¹ in formula (7-3) is as described above, and chlorine is most preferable.

Examples of the transition metal catalyst used in the hydrosilylation reaction are platinum, rhodium, iridium, ruthenium, palladium, molybdenum, iron, cobalt, nickel, manganese and the like. Of these, platinum catalysts are more preferred. These catalysts can be used as a homogeneous catalyst dissolved in a solvent or a solid catalyst supported on carbon or silica. It may be used in the form of coexisting phosphine, amine, potassium acetate and the like. The preferable amount of the transition metal catalyst used is 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol as a transition metal catalyst atom with respect to 1 mol of the Si—H group in the compound (7-3).

It is preferable that the usage-amount of a compound (6-3) is 0.1-5 times by the equivalent ratio with respect to Si-H group of a compound (7-3). Since the hydrosilylation reaction proceeds almost quantitatively, it does not make much sense to change this equivalence ratio greatly. However, if the amount of the compound (7-3) having a large boiling point difference from the target product compound (1-3) is increased, the unreacted compound can be easily distilled off under reduced pressure. Therefore, the amount of compound (6-3) used is the amount of Si in compound (7-3).
The equivalent ratio to the —H group is preferably 0.5 times. And in order to isolate | separate an unreacted raw material compound and solvent from a compound (1-3), in order to prevent that a compound (1-3) is decomposed | disassembled by hold | maintaining on high temperature conditions for a long time, The raw material compound for the reaction, for example, the compound (7-3) and the solvent may be distilled off under reduced pressure.

The present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. The molecular weight data in the examples is a polystyrene conversion value determined by GPC (gel permeation chromatography). The GPC measurement conditions are shown below.
Apparatus: JASCO GULLIVER 1500 (intelligent differential refractometer RI-1530) manufactured by JASCO Corporation
Solvent: Tetrahydrofuran Flow rate: 1 ml / min
Column temperature: 40 ° C
Columns used: Examples 1 to 90: manufactured by Tosoh Corporation, TSKguardcolumn HXL-L (GUARDCOLUMN) + TSKgel G1000HxL (exclusion limit molecular weight (polystyrene): 1,000) + TSkgel G2000HxL (exclusion limit molecular weight (polystyrene): 10,000)
Standard sample for calibration curve: Polymer Laboratories, Polymer Standards (PL), Polystyrene

The meanings of symbols used in the examples are as follows.
Et: ethyl Pr: propyl TFPr: 3,3,3-trifluoropropyl NFHe: nonafluoro-1,1,2,2-tetrahydrohexyl TDFOc: tridecafluoro-1,1,2,2-tetrahydrooctyl TMS: trimethylsilyl Mn: number average molecular weight Mw: weight average molecular weight

[Example 1]
<Synthesis of sodium-bonded 3,3,3-trifluoropropylsilsesquioxane compound from trifluoropropyltrimethoxysilane>
To a 1-liter four-necked flask equipped with a reflux condenser, thermometer and dropping funnel was added trifluoropropyltrimethoxysilane (100 g), THF (500 ml), deionized water (10.5 g) and sodium hydroxide. (7.9 g) was charged and the mixture was heated with an oil bath from room temperature to a temperature at which THF was refluxed while stirring with a magnetic stirrer. Stirring was continued for 5 hours from the start of reflux to complete the reaction. The flask was then lifted from the oil bath and allowed to stand at room temperature overnight, then set in the oil bath again and concentrated by heating under constant pressure until a solid precipitated. The precipitated product was filtered using a pressure filter equipped with a membrane filter having a pore size of 0.5 μm. Next, the obtained solid was washed once with THF and dried in a vacuum dryer at 80 ° C. for 3 hours to obtain 74 g of a colorless powdery solid.

[Example 2]
<Introduction of trimethylsilyl group>
A colorless powdery solid obtained in Example 1 (1.0 g), THF (10 g) and triethylamine (1...) Were placed in a 4-ml flask having an internal volume of 50 ml equipped with a dropping funnel, a reflux condenser and a thermometer. 0 g) was charged and sealed with dry nitrogen. While stirring with a magnetic stirrer, chlorotrimethylsilane (3.3 g) was added dropwise at room temperature over about 1 minute. After completion of the dropping, stirring was continued for another 3 hours at room temperature to complete the reaction. Subsequently, 10 g of pure water was added to hydrolyze the sodium chloride and unreacted chlorotrimethylsilane produced. The reaction mixture thus obtained was transferred to a separatory funnel and separated into an organic phase and an aqueous phase, and the resulting organic phase was repeatedly washed with deionized water until the washing solution became neutral. The obtained organic phase was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure using a rotary evaporator to obtain a white solid compound (0.9 g).
The obtained white powdery solid was subjected to structural analysis by GPC, ¹ H-NMR, ²⁹ Si-NMR and ¹³ C-NMR. From the GPC chart, it was confirmed that the white powdery solid showed monodispersity, the molecular weight was a weight average molecular weight 1570 in terms of polystyrene, and the purity was 98% by weight. ^{From the 1} H-NMR chart, it was confirmed that the trifluoropropyl group and the trimethylsilyl group were present at an integration ratio of 7: 3. ²⁹ Si-NMR chart confirms that there are three peaks that have a trifluoropropyl group and suggest a T structure at a ratio of 1: 3: 3, and one peak that suggests a trimethylsilyl group at 12.11 ppm. It was done. ^{Also in the 13} C-NMR chart, it was confirmed that peaks suggesting a trifluoropropyl group were present at 131 to 123 ppm, 28 to 27 ppm, and 6 to 5 ppm, and a peak suggesting a trimethylsilyl group was present at 1.4 ppm. From the measurement results of the mass spectrometry spectrum, the absolute molecular weight coincided with the theoretical molecular weight of the structure represented by the formula (8). From the result of crystal structure analysis by X-ray structure analysis, it was confirmed that the structure was as shown in Formula (8). These results indicate that the colorless powdery solid which is the object of the structural analysis has the structure of the formula (8). Therefore, the compound before trimethylsilylation is determined to have the structure of formula (9).

[Example 3]
<Synthesis of sodium-bonded nonafluoro-1,1,2,2-tetrahydrohexylsilsesquioxane compound using nonafluoro-1,1,2,2-tetrahydrohexyltrimethoxysilane as a raw material>
To a four-necked flask having an internal volume of 200 ml equipped with a reflux condenser, a thermometer and a dropping funnel, nonafluoro-1,1,2,2-tetrahydrohexyltrimethoxysilane (20.00 g), THF (93.74 g), Sodium hydroxide (0.93 g) and deionized water (1.26 g) were charged and heated with stirring with a magnetic stirrer. Stirring was continued for 5 hours after refluxing started at 64.0 ° C. to complete the reaction. The reaction solution was concentrated until a solid precipitated under normal pressure, and further dried under vacuum to obtain a viscous compound (17.83 g).

[Example 4]
<Introduction of trimethylsilyl group>
A viscous compound obtained in Example 3 (2.0 g), THF (10 g) and triethylamine (0.6 g) were added to a three-necked flask with an internal volume of 50 ml equipped with a dropping funnel, a reflux condenser and a thermometer. And sealed with dry nitrogen. While stirring with a magnetic stirrer, chlorotrimethylsilane (1.7 g) was added dropwise over about 1 minute at room temperature. After completion of the dropwise addition, stirring was continued for 4 hours at room temperature to complete the reaction. Subsequently, 10 g of pure water was added to hydrolyze the sodium chloride and unreacted chlorotrimethylsilane produced. The reaction mixture thus obtained is transferred to a separatory funnel, 30 ml of toluene is added to separate it into an organic phase and an aqueous phase, and the resulting organic phase is washed with deionized water until the washing solution becomes neutral. Repeated. The obtained organic phase was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure using a rotary evaporator to obtain a viscous compound (1.0 g).
The resulting viscous compound was subjected to structural analysis by GPC, ¹ H-NMR and ²⁹ Si-NMR. From the GPC chart, it was confirmed that the viscous compound showed monodispersity and had a purity of 99% by weight. ^{From the 1} H-NMR chart, it was confirmed that a nonafluorohexyl group and a trimethylsilyl group were present at an integration ratio of 7: 3. ²⁹ Si-NMR chart confirms that there are three peaks that have a nonafluorohexyl group and suggest a T structure at a ratio of 1: 3: 3, and one peak that suggests a trimethylsilyl group at 12.52 ppm. It was done. These results show that the viscous compound which is the object of the structural analysis has the structure of the formula (10). Therefore, the compound of Example 3 before trimethylsilylation is judged to have the structure of formula (11).

[Example 5]
<Synthesis of sodium-bound tridecafluoro-1,1,2,2-tetrahydrooctylsilsesquioxane compound using tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane as a raw material>
Into a 50 ml four-necked flask equipped with a reflux condenser, thermometer and dropping funnel, tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane (4.9 g), THF (15 ml), Sodium hydroxide (0.2 g), ion-exchanged water (0.2 g) and a stirring bar were added, and the mixture was heated to reflux at 75 ° C. Stirring was continued for 5 hours from the start of reflux to complete the reaction. Then, the mixture was heated and concentrated under a constant pressure, and dried at 80 ° C. for 3 hours with a vacuum drier to obtain 4.0 g of a viscous liquid.

[Example 6]
<Introduction of trimethylsilyl group>
The above viscous liquid (2.6 g), THF (10 g), triethylamine (1.0 g) and trimethylchlorosilane (3.3 g) are charged into a three-necked flask with an internal volume of 50 ml, and stirred with a magnetic stirrer. The mixture was stirred at room temperature for 3 hours. After completion of the reaction, the same treatment as in the structure confirmation of Example 2 was performed to obtain 1.3 g of a viscous liquid.
The resulting compound was analyzed by GPC. As a result of the measurement, it was confirmed that the viscous liquid was monodispersed and its molecular weight was 100% in terms of polystyrene and a weight average molecular weight of 3650. Judging comprehensively from this result and the result of Example 2, it was estimated that the viscous liquid to be analyzed was a silicon compound represented by the formula (12). Therefore, it is suggested that the compound obtained in Example 5 has a structure represented by the formula (13).

[Example 7]
<Synthesis of Allyl-Heptakis (3,3,3-trifluoropropyl) octasilsesquioxane Using Compound (9) and Allyltrichlorosilane as Raw Materials>
Under a nitrogen atmosphere, a 300 ml three-necked flask was charged with compound (9) (17.2 g), triethylamine (2.30 g) dried with molecular sieves (4A) and dry dichloromethane (250 ml). The compound (9) was dissolved while stirring at room temperature using a magnetic stirrer, and then the system temperature was adjusted to 3 ° C. using an ice bath. Allyltrichlorosilane (3.75 g, 1.4 equivalents relative to compound (9)) was quickly added to this solution, and the mixture was stirred for 1 hour in an ice bath, and further stirred at room temperature for 8 hours. After completion of the reaction, triethylamine-bromide was removed by filtration. The resulting reaction solution was washed three times with water (300 ml) and then dried over anhydrous magnesium sulfate (15 g). The obtained liquid component was freed from the solvent using a rotary evaporator to obtain a white sticky product. To this, 150 ml of methanol and 20 ml of dichloromethane were added to precipitate a solid component. After solid components were sufficiently precipitated, solid-liquid separation was performed by filtration. The obtained solid was dried under reduced pressure (400 Pa, 55 ° C.) to obtain a white solid (9.84 g, yield 57%).

As a result of GPC measurement of the obtained individual, a single peak was confirmed, and the presence of impurities and the like was not confirmed. It was found that the solid obtained from the results of IR, ¹ H-NMR, ¹³ C-NMR and ²⁹ Si-NMR shown below has a structure represented by the formula (14).
IR (KBr method) ν = 2950 (-CH ₃ ), 2926 (-CH _2- ), 1638 (C = C), 1448 (-CH _2- ), 1423 (CH = CH ₂ ), 1375 (-CH ₃ ), 1214 (-CF ₃ ), 1110 (Si-O-Si), 660 (CH = CH ₂ )
¹ H-NMR (400MHz, TMS standard: δ = 0.0ppm): 5.77-5.66 ( m, 1H, Si-CH 2 -C H = CH 2), 5.03-4.99 (m, 2H, Si-CH 2 -CH = C H ₂ ), 2.20-2.08 (m, 14H, Si-CH ₂ -C H ₂ -CF ₃ ), 1.69 (d, 2H,
Si-C H ₂ -CH = CH ₂ ), 0.96-0.91 (m, 14H, Si-C H ₂ -CH ₂ -CF ₃ )
¹³ C-NMR (100MHz, TMS standard: δ = 0.0ppm): 130.5 ( Si-CH 2 - C H = CH 2), 126.9 (Si-CH 2 -CH 2 - C F 3), 116.1 (Si-CH ₂ -CH = C H ₂ ), 27.6 (Si-CH ₂ - C H ₂ -CF ₃ ), 18.8 (Si- C H ₂ -CH = CH ₂ ), 3.99 (Si- C H ₂ -CH ₂ -CF ₃ )
²⁹ Si-NMR (79 MHz, TMS standard: δ = 0.0 ppm): -67.46, -67.51, -70.2

[Example 8]
<Synthesis of vinyl-heptakis (3,3,3-trifluoropropyl) octasilsesquioxane using compound (9) and vinyltrichlorosilane as raw materials>
A compound represented by the formula (15) can be obtained by performing the same operation as in Example 7 except that vinyltrichlorosilane is used instead of allyltrichlorosilane.

[Example 9]
<Synthesis of 5-hexenyl-heptakis (3,3,3-trifluoropropyl) octasilsesquioxane from Compound (9) and 5-hexenyltrichlorosilane>
A compound represented by the formula (16) can be obtained by performing the same operation as in Example 7 except that 5-hexenyltrichlorosilane is used instead of allyltrichlorosilane.

[Example 10]
<Synthesis of Allyl-Heptakis (Nonafluoro-1,1,2,2-tetrahydrohexyl) octasilsesquioxane from Compound (11) and Allyltrichlorosilane>
A compound represented by the formula (17) can be obtained by performing the same operation as in Example 7 except that the compound (11) is used in place of the compound (9).

[Example 11]
<Synthesis of vinyl-heptakis (nonafluoro-1,1,2,2-tetrahydrohexyl) octasilsesquioxane using compound (11) and vinyltrichlorosilane as raw materials>
A compound represented by the formula (18) is obtained by performing the same operation as in Example 7 except that the compound (11) is used instead of the compound (9) and vinyltrichlorosilane is used instead of allyltrichlorosilane. Can do.

[Example 12]
<Synthesis of 5-hexenyl-heptakis (nonafluoro-1,1,2,2-tetrahydrohexyl) octasilsesquioxane from compound (11) and 5-hexenyltrichlorosilane>
The compound represented by the formula (19) is obtained by performing the same operation as in Example 7 except that the compound (11) is used instead of the compound (9) and 5-hexenyltrichlorosilane is used instead of allyltrichlorosilane. Obtainable.

[Example 13]
<Synthesis of Allyl-Heptakis (Tridecafluoro-1,1,2,2-tetrahydrooctyl) octasilsesquioxane from Compound (13) and Allyltrichlorosilane>
A compound represented by the formula (20) can be obtained by performing the same operation as in Example 7 except that the compound (13) is used instead of the compound (9).

[Example 14]
<Synthesis of vinyl-heptakis (tridecafluoro-1,1,2,2-tetrahydrooctyl) octasilsesquioxane using compound (13) and vinyltrichlorosilane as raw materials>
A compound represented by the formula (21) is obtained by performing the same operation as in Example 7 except that the compound (13) is used instead of the compound (9) and vinyltrichlorosilane is used instead of allyltrichlorosilane. Can do.

[Example 15]
<Synthesis of 5-hexenyl-heptakis (tridecafluoro-1,1,2,2-tetrahydrooctyl) octasilsesquioxane using compound (13) and 5-hexenyltrichlorosilane as raw materials>
The compound represented by the formula (22) is obtained by performing the same operation as in Example 7 except that the compound (13) is used instead of the compound (9) and 5-hexenyltrichlorosilane is used instead of allyltrichlorosilane. Obtainable.

[Example 16]
<Synthesis of silanol-containing heptakis (3,3,3-trifluoropropyl) silsesquioxane compound from compound (9)>
A 300 ml four-necked flask equipped with a dropping funnel, reflux condenser, thermometer and stir bar was placed in an ice bath. 5 g of the compound (9) obtained in Example 1 was placed in this four-necked flask and dissolved in butyl acetate (50 g), and then acetic acid (0.5 g) was added dropwise. The mixture was stirred for 1 hour in an ice bath. After returning to room temperature, the reaction solution was washed (3 times) with deionized water (100 ml). The solvent was distilled off using a rotary evaporator, and vacuum drying (450 Pa, 50 ° C., 1 hour) was performed as it was to obtain a viscous liquid (4.3 g). As a result of GPC measurement of the obtained compound, a single peak was shown and the presence of impurities and the like was not confirmed. As a result of further analysis using IR, absorption (near 3400 cm ⁻¹ ) suggesting the presence of a silanol group that was not observed in the compound (9) was confirmed. Therefore, it was suggested that the obtained compound has a structure represented by the formula (23).

  The compound (23) is used as a starting material in place of the compound (9), and is reacted in the presence of triethylamine according to the methods described in Examples 7 to 9, whereby the compound (14) to the compound ( 16) can be induced.

[Example 17]
<Synthesis of 3-trichlorosilanylpropyl-heptakis (3,3,3-trifluoropropyl) octasilsesquioxane>
Under a nitrogen atmosphere, compound (14) (0.90 g) was charged into a 100 ml three-necked flask equipped with a reflux condenser and a thermometer, and dry tetrahydrofuran (6.0 ml) was added and dissolved. The system temperature was kept at about 20 ° C. using a water bath, and trichlorosilane (TCS, 0.4 ml, TCS / compound (15) molar ratio = 4.2) was introduced all at once here. A Pt catalyst / xylene solution (25 μl, Pt content: 3 wt .-%, Pt / Si—H molar ratio = 9.8 × 10 ⁻⁴ ) was added thereto. After adding the catalyst, the water bath was removed and the mixture was stirred at room temperature for 2.5 hours. Unreacted TCS remaining in the reaction solution was distilled off under reduced pressure using a vacuum pump, and then dried under reduced pressure (400 Pa, 75 ° C.) to obtain a solid (0.98 g, yield: 98%).

The obtained solid was subjected to ¹ H-NMR measurement, and it was found that the obtained solid had a structure represented by the formula (24) because the disappearance of the raw material signal and the presence of impurities and the like were not confirmed. ¹ H-NMR (400MHz, TMS standard: δ = 0.0ppm): 2.26-2.17 ( m, 14H, Si-CH 2 -C H 2 -CF 3), 1.81-1.77 (m, 2H, Si-CH 2 - C H ₂ —CH ₂ —SiCl ₃ ), 1.51 (t, 2H, Si—CH ₂ —CH ₂ —C H ₂ —SiCl ₃ ), 1.05-1.01 (m, 14H, Si—C H ₂ —CH ₂ — CF ₃ ), 0.94 (t, 2H, Si—C H ₂ —CH ₂ —CH ₂ —SiCl ₃ )

[Example 18]
<Synthesis of 2-trichlorosilanylethyl-heptakis (3,3,3-trifluoropropyl) octasilsesquioxane>
A compound represented by the formula (25) can be obtained by performing the same operation as in Example 17 except that the compound (15) is used in place of the compound (14).

[Example 19]
<Synthesis of 6-trichlorosilanylhexyl-heptakis (3,3,3-trifluoropropyl) octasilsesquioxane>
A compound represented by the formula (26) can be obtained by performing the same operation as in Example 17 except that the compound (16) is used in place of the compound (14).

[Example 20]
<Synthesis of 3-trichlorosilanylpropyl-heptakis (nonafluoro-1,1,2,2-tetrahydrohexyl) octasilsesquioxane>
A compound represented by the formula (27) can be obtained by performing the same operation as in Example 17 except that the compound (17) is used in place of the compound (14).

[Example 21]
<Synthesis of 2-trichlorosilanylethyl-heptakis (nonafluoro-1,1,2,2-tetrahydrohexyl) octasilsesquioxane>
A compound represented by the formula (28) can be obtained by performing the same operation as in Example 17 except that the compound (18) is used instead of the compound (14).

[Example 22]
<Synthesis of 6-trichlorosilanylhexyl-heptakis (nonafluoro-1,1,2,2-tetrahydrohexyl) octasilsesquioxane>
A compound represented by the formula (29) can be obtained by performing the same operation as in Example 17 except that the compound (19) is used instead of the compound (14).

[Example 23]
<Synthesis of 3-trichlorosilanylpropyl-heptakis (tridecafluoro-1,1,2,2-tetrahydrooctyl) octasilsesquioxane>
A compound represented by the formula (30) can be obtained by performing the same operation as in Example 17 except that the compound (20) is used in place of the compound (14).

[Example 24]
<Synthesis of 2-trichlorosilanylethyl-heptakis (tridecafluoro-1,1,2,2-tetrahydrooctyl) octasilsesquioxane>
A compound represented by the formula (31) can be obtained by performing the same operation as in Example 17 except that the compound (21) is used in place of the compound (14).

[Example 25]
<Synthesis of 6-trichlorosilanylhexyl-heptakis (tridecafluoro-1,1,2,2-tetrahydrooctyl) octasilsesquioxane>
A compound represented by the formula (32) can be obtained by performing the same operation as in Example 17 except that the compound (22) is used in place of the compound (14).

Claims (14)

Silicon compound represented by formula (1):

Here, A is a group represented by the following formula (2) ; R ¹ is a group independently selected from alkyl, aryl and arylalkyl having 1 to 40 carbon atoms, each of which is at least 1 A group in which one hydrogen is replaced by fluorine; in the alkyl having 1 to 40 carbon atoms, any —CH ₂ — may be replaced by —O—, cycloalkylene or phenylene; in this arylalkyl, —CH ₂ — may be replaced by —O—, cycloalkylene or phenylene.

Here, Z ¹ is alkylene having 2 to 10 carbons, and any —CH ₂ — in the alkylene may be replaced by —O— or phenylene; R ² is alkyl having 1 to 20 carbons ; An aryl having 6 to 20 carbon atoms or an arylalkyl having 7 to 20 carbon atoms; X
¹ is halogen; and n is an integer from 0 to 2. R ¹ in the formula (1) according to claim 1 is a fluoroalkyl having 1 to 20 carbon atoms, A compound according to claim 1. R ¹ in formula (1) according to claim ¹ is 2-fluoroethyl, 2,2-difluoroethyl, 3,3,3-trifluoropropyl, nonafluoro-1,1,2,2-tetrahydrohexyl, tri Decafluoro-1,1,2,2-tetrahydrooctyl, hepadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H-dodecyl or perfluoro-1H, 1H, 2H a 2H- tetradecyl a compound according to claim 1. R ¹ in formula (1) according to claim ¹ is 3,3,3-trifluoropropyl, nonafluoro-1,1,2,2-tetrahydrohexyl or tridecafluoro-1,1,2,2-tetrahydro. octyl a compound according to claim 1. The compound according to claim 1, wherein R ¹ in formula (1) according to claim ¹ is 3,3,3-trifluoropropyl or nonafluoro-1,1,2,2-tetrahydrohexyl. The compound according to claim 1, wherein Z ¹ is alkylene having 2 to 8 carbons; and n is 0 or 1. The compound according to claim 1, wherein Z ¹ is alkylene having 2 to 4 carbons; and n is 0 or 1. R ¹ in formula (1) according to claim ¹ is 3,3,3-trifluoropropyl; Z ¹ in formula (2) is alkylene having 2 or 3 carbon atoms; and n is 0 The compound according to claim 1 . The method for producing a silicon compound represented by the formula (1-1), wherein the step (b) is carried out following the step (a1):

Wherein R ¹ is a group independently selected from alkyl having 1 to 40 carbons, aryl and arylalkyl, each of which is a group in which at least one hydrogen is replaced by fluorine; In the alkyl group of 1 to 40, any —CH ₂ — may be replaced by —O—, cycloalkylene, or phenylene; in this arylalkyl, any —CH ₂ — represents —O—, cycloalkylene, or phenylene. Z ³ is a single bond or alkylene having 1 to 8 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O— or phenylene; R ² is carbon Number 1
˜20 alkyl, C 6-20 aryl or C 7-20 arylalkyl; X ¹ is halogen; and n is an integer of 0-2.

<Step (a1)>
A step of obtaining a compound represented by the formula (6) by reacting a compound represented by the formula (3) with a compound represented by the formula (5):

Here, M is a monovalent alkali metal atom; X ² is halogen; and R ¹ and Z ³ have the same meaning as R ¹ and Z ³ in formula (1-1), respectively.
<Step (b)>
A step of obtaining a compound represented by the formula (1-1) by reacting a compound represented by the formula (6) with a compound represented by the formula (7) in the presence of a transition metal catalyst:

Here, R ² and X ¹ have the respective same meaning as R ² and X ¹ in formula (1-1). The method for producing a silicon compound represented by the formula (1-1), wherein the step (b) is carried out following the step (a2):

Wherein R ¹ is a group independently selected from alkyl having 1 to 40 carbons, aryl and arylalkyl, each of which is a group in which at least one hydrogen is replaced by fluorine; In the alkyl group of 1 to 40, any —CH ₂ — may be replaced by —O—, cycloalkylene, or phenylene; in this arylalkyl, any —CH ₂ — represents —O—, cycloalkylene, or phenylene. Z ³ is a single bond or alkylene having 1 to 8 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O— or phenylene; R ² is carbon C 1 -C 20 alkyl, aryl alkyl aryl or 7 to 20 carbon atoms having 6 to 20 carbon atoms; X ¹ is halogen And, n represents an integer of 0 to 2.
<Step (a2)>
A step of obtaining a compound represented by the formula (6) by reacting a compound represented by the formula (4) with a compound represented by the formula (5):

Where X ² is halogen; and R ¹ and Z ³ have the same meaning as R ¹ and Z ³ in formula (1-1), respectively.
<Step (b)>
A step of obtaining a compound represented by the formula (1-1) by reacting a compound represented by the formula (6) with a compound represented by the formula (7) in the presence of a transition metal catalyst:

Here, R ² and X ¹ have the respective same meaning as R ² and X ¹ in formula (1-1). In the formula (1-1), R ¹ is 2-fluoroethyl, 2,2-difluoroethyl, 3,3,3-trifluoropropyl, nonafluoro-1,1,2,2-tetrahydrohexyl, tridecafluoro-1 , 1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H-dodecyl or perfluoro-1H, 1H, 2H, 2H-tetradecyl The manufacturing method according to claim 9 or 10 , wherein In the formula (1-1), R ¹ is 3,3,3-trifluoropropyl or nonafluoro-
The production method according to claim 9 or 10 , which is 1,1,2,2-tetrahydrohexyl; and n is 0 or 1. The silane coupling agent containing the silicon compound of any one of Claims 1-8 . The solid surface treating agent containing the silicon compound of any one of Claims 1-8 .