JP2019189564A - Silsesquioxane derivative containing alkoxysilyl group - Google Patents

Abstract

To provide a silsesquioxane derivative containing an alkoxysilyl group that prevents coupling of molecules.SOLUTION: The present invention provides a silsesquioxane represented by formula (I) (each R: a hydrocarbon group or a fluorinated alkyl, each Y: -(CH)-Si(OR), -(CH)-S-(CH)-Si(OR), -(CH)-S-(CH)-Si(OR)CH, or -Si-Z(CH), m and n: an integer of 1 to 4, each R: methyl or ethyl).SELECTED DRAWING: None

Description

  The present invention relates to a silsesquioxane derivative containing an alkoxysilyl group.

  Cage-type silsesquioxane (POSS) is attracting attention as a nano building block for organic and inorganic hybrid materials. On the other hand, fluoroalkyl compounds are chemically stable, excellent in heat resistance, chemical resistance, weather resistance, and acid resistance, and have low intermolecular cohesion and low surface free energy, so they have excellent water and oil repellency. , Non-adhesive and antifouling properties can be obtained. The fluorine-containing silane coupling agent is designed so that the fluorine-containing organic group in the molecule is responsible for imparting properties, and another functional group in the same molecule reacts with the hydroxyl group on the solid surface. Has been used. The fluorine-containing cage-type silsesquioxane compound has a structure in which a large number of fluorine-containing groups are introduced into a rigid and bulky dice-like inorganic skeleton at a high density, so that even a short perfluoroalkyl chain has molecular mobility. A material that is suppressed and has the above properties more emphasized can be obtained. For this reason, a silane coupling agent having an alkoxysilyl group introduced into a fluorine-containing cage-type silsesquioxane compound has been developed and applied to a tough coating film (Patent Document 1).

  However, since the above functional group in the fluorine-containing silane coupling agent of Patent Document 1 is a silanol group in an aqueous solution, the fluorine-containing organic group is effectively uniform on the solid surface due to a reaction between the coupling agents. The coating cannot be applied.

  In addition, introduction of an alkoxysilyl group into a fluorine-containing cage silsesquioxane compound is limited to one function (Patent Document 2). In this case, it is difficult to obtain an amorphous optically transparent material containing the fluorine-containing cage silsesquioxane compound at a high density because of the high crystallinity of the fluorine-containing cage silsesquioxane compound. Moreover, since the cage silsesquioxane compound into which these alkoxysilyl groups are introduced is solid at room temperature, an organic solvent is essential as a cosolvent in order to advance the sol-gel reaction.

JP 2014-152246 JP2007-15977

  One object of the present invention is to provide a silsesquioxane having an alkoxysilyl group that hardly causes a reaction between coupling agents.

  Another object of the present invention is to provide a silsesquioxane having an alkoxysilyl group that is liquid or semi-solid at room temperature and in which a sol-gel reaction proceeds without solvent.

  In order to achieve the above object, the present inventors have reacted a plurality of alkoxysilanes with a silsesquioxane compound to form a functional new material, incompletely condensed silsesquioxane silane (Incompletely consdensed POSS, IC- POSS) successfully developed a coupling agent. This novel silane coupling agent is soluble in various organic solvents and has fluidity at room temperature, so that sol-gel reaction is possible even without solvent.

According to the present invention, the following aspects are provided.
[1] Silsesquioxane represented by the formula (I).

(In the formula, each R ¹ independently represents a hydrocarbon group or a fluorinated alkyl,
Each Y independently represents — (CH ₂ ) _m —Si (OR ² ) ₃ ,
_{- (CH 2) m -S- (} CH 2) n -Si (OR 2) 3,
_{- (CH 2) m -S- (} CH 2) n -Si (OR 2) 2 CH 3 , or -Si-Z (CH _{3), 2,}
m and n are each independently an integer from 1 to 4,
Each R ² is independently methyl or ethyl;
Z is — (CH ₂ ) _p —Si (OR) ₃ ,
_{- (CH 2) p -S- (} CH 2) q -Si (OR 3) 3,
_{- (CH 2) p -S- (} CH 2) q -Si (OR 3) 2 CH 3,
_{- (CH 2) s -O-} CO (NH) - (CH 2) t -Si (OR 3) 3 or,
_{- (CH 2) s -O-} CO (NH) - (CH 2) t -Si (OR 3) a ₂ CH _3,
p and q are each independently an integer from 1 to 4,
s and t are each independently an integer from 1 to 6;
Each R ³ is independently methyl or ethyl. )
[2] Each R ¹ is independently

And
Each Y independently represents — (CH ₂ ) _m —Si (OR ² ) ₃ ,
_{- (CH 2) m -S- (} CH 2) n -Si (OR 2) 3, or _{- (CH 2) m -S- (} CH 2) n -Si (OR 2) a ₂ CH _3,
m and n are each independently an integer from 1 to 4,
Each R ² is independently silsesquioxane according to [1], which is methyl or ethyl.
[3] The silsesquioxane according to [1] represented by the formula (II).

(In the formula, each R ¹ independently represents a hydrocarbon group or a fluorinated alkyl,
Each Z is, _{independently, - (CH 2) p -Si} (OR 3) 3,
_{- (CH 2) p -S- (} CH 2) q -Si (OR 3) 3,
_{- (CH 2) p -S- (} CH 2) q -Si (OR 3) 2 CH 3,
_{- (CH 2) s -O-} CO (NH) - (CH 2) t -Si (OR 3) 3 or,
_{- (CH 2) s -O-} CO (NH) - (CH 2) t -Si (OR 3) a ₂ CH _3,
Where p and q are each independently an integer from 1 to 4,
s and t are each independently an integer from 1 to 6;
Each R ³ is independently methyl or ethyl. )
[4] An optically transparent material comprising the silsesquioxane polymer according to any one of [1] to [3].

  According to the silsesquioxane of the present invention, a more uniform coating including a surface modifier can be provided. Moreover, since a sol-gel reaction can be caused without using an organic solvent, it can be used for production of various materials such as an optically transparent material and a high water vapor barrier material.

¹ H-NMR spectrum of IC-POSS (Compound 1) of Example 1. IC-POSS of Example 1 (Compound 1) ²⁹ Si-NMR spectrum. ¹ H-NMR spectrum of IC-POSS (Compound 2) of Example 2. ²⁹ Si-NMR spectrum of IC-POSS (Compound 2) of Example 2. The photograph of the glass-like transparent material manufactured from the fluorine-containing silsesquioxane of Example 3.

  In this specification, “normal temperature” refers to 20 ° C.

  In this specification, “transparent” means that the average transmittance in the visible light region is 80% or more, preferably 90% or more.

  In this specification, “semi-transparent” means that the average transmittance in the visible light region is less than 80% and does not completely cover the base, and preferably the average transmittance in the visible light region is 30%. ~ 70%.

  In this specification, “semi-solid” refers to a state having both properties of liquid and solid.

  The silsesquioxane of the present invention is represented by the following formula (I). The silsesquioxane of the present invention is an incompletely condensed silsesquioxane silane (IC-POSS) having a structure in which one apex of a cage silsesquioxane (POSS) is missing. For this reason, the functional group bonded to silicon has the same heat resistance as the cage-type silsesquioxane, but the crystallinity is lowered.

  The silsesquioxane of the present invention is represented by the following formula (I).

In the formula, each R ¹ independently represents a hydrocarbon group or an alkyl fluoride,
Each Y is _{independently, - (CH 2) m -Si} (OR 2) 3, - (CH 2) m -S- (CH 2) n -Si (OR 2) 3, - (CH 2) m _{-S- (CH 2) n -Si (} oR 2) 2 CH 3 , or -Si-Z (CH _{3), 2,}
m and n are each independently an integer from 1 to 4,
Each R ² is independently methyl or ethyl;
Z _{is, - (CH 2) p -Si} (OR 3) 3,
_{- (CH 2) p -S- (} CH 2) q -Si (OR 3) 3,
_{- (CH 2) p -S- (} CH 2) q -Si (OR 3) 2 CH 3,
_{- (CH 2) s -O-} CO (NH) - (CH 2) t -Si (OR 3) 3 or,
_{- (CH 2) s -O-} CO (NH) - (CH 2) t -Si (OR 3) a ₂ CH _3,
p and q are each independently an integer from 1 to 4,
s and t are each independently an integer from 1 to 6;
Each R ³ is independently methyl or ethyl.

When R ¹ is a hydrocarbon group, R ¹ may be either a saturated hydrocarbon or an unsaturated hydrocarbon. R ¹ may be aliphatic acyclic (that is, a linear or branched hydrocarbon group), aliphatic cyclic (that is, an alicyclic hydrocarbon group), and aromatic. The formula aliphatic and cycloaliphatic may be either saturated or unsaturated.

When R ¹ is aliphatic acyclic, the carbon number is preferably 1 to 10, and more preferably 1 to 6. When R ¹ is alkyl, examples of R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, heptyl and the like. When R ¹ is aliphatic cyclic, the number of carbon atoms is preferably 1 to 10, and more preferably 1 to 6. Examples of such aliphatic cyclic R ¹ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like. When R ¹ is an aromatic hydrocarbon group, the carbon number is preferably 4 to 15 and more preferably 5 to 8. Examples of R ¹ of such an aromatic hydrocarbon group include a phenyl group and a benzyl group.

When R ¹ is fluorinated alkyl, the carbon number of R ¹ is preferably 1 to 10 and more preferably 1 to 6 in consideration of solubility in a solvent. R ¹ may be linear or branched. Examples of the alkyl of R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, heptyl and the like. The number of fluorine in R ¹ may be 1, 2, 3, 4, 5, or more. Examples of linear R ¹ include —CH ₂ CH ₂ CF ₃ , —CH ₂ CH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ CF ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ CF ₂ CF ₂ CF _2. CF ₃ , —CH ₂ CH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ as an example of branched R ¹ CF (CF ₃ ) ₂ , —CH ₂ CH (CF ₃ ) CF ₂ CF ₃ , —CH (CF ₃ ) CH ₂ CF ₂ CF ₃ , —CH ₂ C (CF ₃ ) ₂ CF ₃ , —C (CF _{3 ) 2 CH 2 CF 3 -CH 2} CH 2 CF 2 CF (CF 3) 2, -CH 2 CH 2 CF (CF 3) CF 2 CF 3, -CH 2 CH 2 C (CF 3) or the like ₂ CF ₃ is Can be mentioned.

R ¹ can be perfluoroalkyl (the functional groups bonded to the carbon of R ¹ are all fluorine). Examples of such R ¹ include —CF ₃ , —CF ₂ CF ₃ , —CF ₂ CF ₂ CF ₃ , —CF (CF ₃ ) ₂ , —CF ₂ CF ₂ CF ₂ CF ₃ , —CF ₂ CF _{(CF 3) 2, -C (} CF 3) 3, - (CF 2) 4 CF 3, - (CF 2) 2 CF (CF 3) 2, -CF 2 C (CF 3) 3, -CF (CF _{3) CF 2 CF 2 CF 3} , - (CF 2) 5 CF 3, - (CF 2) 3 CF (CF3) 2, - (CF 2) 4 CF (CF 3) 2, - (CF 2) 7 CF _{3, - (CF 2) 5} CF (CF 3) 2, - (CF 2) 6 CF (CF 3) 2, - (CF 2) 9 CF 3 , and the like.

When R ¹ is fluorinated alkyl, silsesquioxane is an incompletely condensed silsesquioxane silane coupling agent having a fluorinated alkyl group. Such a novel silane coupling agent is soluble in various organic solvents and has fluidity at room temperature, so that a sol-gel reaction is possible even without a solvent. In addition, the new silane coupling agent has excellent water repellency, oil repellency, antifouling property, heat resistance, and low refractive index, so it can be used for coating film, resin or glass surface modification, optical It can use suitably for uses, such as a transparent material.

R ¹ may be different from each other, at least a part thereof may be the same, or all may be the same, but R ¹ is preferably the same from the viewpoint of ease of production.

Each Y may be different from each other, at least a part thereof may be the same, or all may be the same, but R ¹ is preferably the same from the viewpoint of ease of production.

When Y is — (CH ₂ ) _m —Si (OR ² ) ₃ , m is 1, 2, 3 or 4, and preferably m is 1 or 2. Each R ² can independently be methyl or ethyl. R ² may be different from each other, at least a part thereof may be the same, or all may be the same, but R ² is preferably the same from the viewpoint of ease of production.

When Y is — (CH ₂ ) _m —S— (CH ₂ ) _n —Si (OR ² ) ₃ , m is 1, 2, 3 or 4 and n is 1, 2, 3 or 4. Preferably, m is 1 or 2, and n is 1, 2, 3 or 4. Each R ² can independently be methyl or ethyl. R ² may be different from each other, at least a part thereof may be the same, or all may be the same, but R ² is preferably the same from the viewpoint of ease of production.

When Y is — (CH ₂ ) _m —S— (CH ₂ ) _n —Si (OR ² ) ₂ CH ₃ , m is 1, 2, 3 or 4 and n is 1, 2, 3 or 4, preferably m is 1 or 2, and n is 1, 2, 3 or 4. Each R ² can independently be methyl or ethyl. R ² may be different from each other, at least a part thereof may be the same, or all may be the same, but R ² is preferably the same from the viewpoint of ease of production.

When Y is _{-Si-Z (CH 3) 2} , Z _{is, - (CH 2) p -Si} (OR 3) 3, - (CH 2) p -S- (CH 2) q -Si (OR ^{_{3) 3, - (CH 2}} ) p -S- (CH 2) q -Si (OR 3) 2 CH 3, - (CH 2) s -O-CO (NH) - (CH 2) t -Si ( OR ³ ) ₃ or — (CH ₂ ) _s —O—CO (NH) — (CH ₂ ) _t —Si (OR ³ ) ₂ CH ₃ .

When Z is — (CH ₂ ) _p —Si (OR ³ ) ₃ , p is 1, 2, 3 or 4, and preferably p is 1 or 2. Each R ³ can independently be methyl or ethyl. R ³ may be different from each other, at least a part thereof may be the same, or all may be the same, but R ³ is preferably the same from the viewpoint of ease of production.

When Z is — (CH ₂ ) _p —S— (CH ₂ ) _q —Si (OR ³ ) ₃ , p is 1, 2, 3 or 4 and q is 1, 2, 3 or 4. Preferably, p is 1 or 2, and q is 1, 2, 3 or 4. Each R ³ can independently be methyl or ethyl. R ³ may be different from each other, at least a part thereof may be the same, or all may be the same, but R ³ is preferably the same from the viewpoint of ease of production.

When Z is — (CH ₂ ) _p —S— (CH ₂ ) _q —Si (OR ³ ) ₂ CH ₃ , p is 1, 2, 3 or 4 and q is 1, 2, 3 or 4, preferably p is 1 or 2, and q is 1, 2, 3 or 4. Each R ³ can independently be methyl or ethyl. R ³ may be different from each other, at least a part thereof may be the same, or all may be the same, but R ³ is preferably the same from the viewpoint of ease of production.

Z is _{- (CH 2) s -O-} CO (NH) - (CH 2) t -Si case (OR ³⁾ is _3, s is 3, 4, 5 or 6, and t Is 1, 2, 3, 4, 5 or 6, preferably s is 1, 2, 3, or 4 and t is 1, 2, 3, or 4. Each R ³ can independently be methyl or ethyl. R ³ may be different from each other, at least a part thereof may be the same, or all may be the same, but R ³ is preferably the same from the viewpoint of ease of production.

When Z is — (CH ₂ ) _s —O—CO (NH) — (CH ₂ ) _t —Si (OR ³ ) ₂ CH ₃ , s is 1, _{2, 3} , 4, 5 or 6; And t is 1, 2, 3, 4, 5 or 6, preferably s is 1, 2, 3, or 4, and t is 1, 2, 3, or 4. Each R ³ can independently be methyl or ethyl. R ³ may be different from each other, at least a part thereof may be the same, or all may be the same, but R ³ is preferably the same from the viewpoint of ease of production.

  The silsesquioxane of the present invention is preferably liquid or semi-solid at room temperature. For this reason, sol-gel reaction can be advanced without solvent without using an organic solvent.

  The silsesquioxane of the present invention is preferably transparent or translucent. For this reason, it can be suitably used for applications requiring transparency or translucency, such as optically transparent materials.

In one embodiment, each R ¹ is each independently

And each Y independently represents — (CH ₂ ) _m —Si (OR ² ) ₃ , — (CH ₂ ) _m —S— (CH ₂ ) _n —Si (OR ² ) ₃ , or — ( _{CH 2) m -S- (CH 2} ) n -Si (OR 2) a ₂ CH _3.

m and n are each independently an integer from 1 to 4, and each R ² is independently methyl or ethyl.

When Y is — (CH ₂ ) _m —Si (OR ² ) ₃ , m is 1, 2, 3 or 4, and preferably m is 1 or 2. Each R ² can independently be methyl or ethyl. R ² may be different from each other, at least a part thereof may be the same, or all may be the same, but R ² is preferably the same from the viewpoint of ease of production.

When Y is — (CH ₂ ) _m —S— (CH ₂ ) _n —Si (OR ² ) ₃ , m is 1, 2, 3 or 4 and n is 1, 2, 3 or 4. Preferably, m is 1 or 2, and n is 1, 2, 3 or 4. Each R ² can independently be methyl or ethyl. R ² may be different from each other, at least a part thereof may be the same, or all may be the same, but R ² is preferably the same from the viewpoint of ease of production.

When Y is — (CH ₂ ) _m —S— (CH ₂ ) _n —Si (OR ² ) ₂ CH ₃ , m is 1, 2, 3 or 4 and n is 1, 2, 3 or 4, preferably m is 1 or 2, and n is 1, 2, 3 or 4. Each R ² can independently be methyl or ethyl. R ² may be different from each other, at least a part thereof may be the same, or all may be the same, but R ² is preferably the same from the viewpoint of ease of production.

  According to such a configuration, a silsesquioxane having an alkoxysilyl group that is liquid or semi-solid at room temperature and in which a sol-gel reaction proceeds without solvent is provided.

  In another embodiment, the silsesquioxane of the present invention is represented by formula (II).

In the formula, each R ¹ independently represents a hydrocarbon group or an alkyl fluoride,
Each Z is, _{independently, - (CH 2) p -Si} (OR 3) 3,
_{- (CH 2) p -S- (} CH 2) q -Si (OR 3) 3,
_{- (CH 2) p -S- (} CH 2) q -Si (OR 3) 2 CH 3,
_{- (CH 2) s -O-} CO (NH) - (CH 2) t -Si (OR 3) 3 or,
_{- (CH 2) s -O-} CO (NH) - (CH 2) t -Si (OR 3) a ₂ CH _3,
In which p and q are each independently an integer from 1 to 4, s and t are each independently an integer from 1 to 6, and each R ³ is independently methyl or Ethyl.

When each Z is independently — (CH ₂ ) _p —Si (OR ³ ) ₃ , p is 1, 2, 3 or 4, preferably p is 1 or 2. Each R ³ can independently be methyl or ethyl.

When each Z is independently — (CH ₂ ) _p —S— (CH ₂ ) _q —Si (OR ³ ) ₃ , p is 1, 2, 3 or 4 and q is 1, 2, 3 or 4, preferably p is 1 or 2, and q is 1, 2, 3 or 4. Each R ³ can independently be methyl or ethyl.

When each Z is independently — (CH ₂ ) _p —S— (CH ₂ ) _q —Si (OR ³ ) ₂ CH ₃ , p is 1, 2, 3 or 4 and q is 1, 2, 3 or 4, preferably p is 1 or 2, and q is 1, 2, 3 or 4. Each R ³ can independently be methyl or ethyl.

When each Z is independently — (CH ₂ ) _s —O—CO (NH) — (CH ₂ ) _t —Si (OR ³ ) ₃ , s is 1, 2, ₃ , 4, 5 or 6 and t is 1, 2, 3, 4, 5 or 6, preferably s is 1, 2, 3, or 4 and t is 1, 2, 3, or 4. Each R ³ can independently be methyl or ethyl.

Each Z is independently _{- (CH 2) s -O-} CO (NH) - (CH 2) t -Si When a ^{_{(OR 3) 2 CH 3,}} s is 3, 4, 5 or 6, and t Is 1, 2, 3, 4, 5 or 6, preferably s is 1, 2, 3, or 4 and t is 1, 2, 3, or 4. Each R ³ can independently be methyl or ethyl.

R ³ is as described above.

  According to such a configuration, a silsesquioxane having an alkoxysilyl group that is liquid or semi-solid at room temperature and in which a sol-gel reaction proceeds without solvent is provided.

  The present invention also includes a method for producing the above silsesquioxane of the present invention.

  The present inventors have succeeded in producing silsesquioxane of the above formula (I) by reacting incompletely condensed silsesquioxane with alkoxysilane. Known incompletely condensed silsesquioxanes may be used.

  In one embodiment, the silsesquioxane of formula (I) is the opposite of the three Si-bonded vinyl groups near the missing apex of the incompletely condensed silsesquioxane and the alkoxysilyl group of the alkoxysilane. It is synthesized by bonding with a thiol group at the side end.

In another embodiment, the silsesquioxane of formula (I) is
The alkoxysilane to be reacted with the incompletely condensed silsesquioxane is a Si-H formed by Si of each of three Si near the deficient apex of the incompletely condensed silsesquioxane and a hydrogen group bonded thereto. And a vinyl group at the end of the alkoxysilane opposite to the alkoxysilyl group.

  According to the method for producing silsesquioxane of the present invention, silsesquioxane can be produced in high yield. The yield is preferably 60% or more, more preferably 70% or more, and still more preferably 78% or more.

  The present invention also includes an optically transparent material containing the above-described silsesquioxane polymer of the present invention.

  The refractive index of the optically transparent material of the present invention is not limited, but is preferably 1.2 to 1.5, more preferably 1.25 to 1.35. The optically transparent material of the present invention can achieve a low refractive index.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

Example 1
Tris (dimethylvinylsiloxy) heptatrifluoropropyl incomplete POSS (0.112 g, 0.084 mmol) and 2,2'-azobisisobutyronitrile (AIBN) (0.0007 g, 0.0038 mmol) in anhydrous tetrahydrofuran (THF) (0.75 ml) To the solution was added 3-mercaptopropyltrimethoxylane (0.23 ml, 1.26 mmol) under a nitrogen atmosphere. After reacting the reaction solution at 80 ° C. for 6 hours, volatile components were distilled off under reduced pressure. The obtained residue was purified by HPLC to obtain a colorless semi-solid product 1 in a yield of 78% (0.0903 g, 0.047 mmol) (FIGS. 1 and 2).

¹ H-HMR (in CDCl ₃ , 400MHz): δ 3.58-3.54 (m, 27H, -Si- (OC H ₃ ) ₃ ); 2.26-2.51 (m, 12H, Si (CH ₃ ) ₂ -CH _2- C H ₂ -SC H ₂ -CH ₂ -CH ₂ -Si- (O-CH ₃ ) ₃ ); 2.10-2.09, (m, 14H, Si-CH ₂ -C H ₂ -CF ₃ ); 1.70-1.68 (m, 6H, Si (CH ₃ ) ₂ -C H ₂ -CH ₂ -S-CH ₂ -CH ₂ -CH ₂ -Si- (O-CH ₃ ) ₃ ); 0.97-0.72 (m, 26H, Si (CH ₃ ) ₂ -CH ₂ -CH ₂ -S-CH ₂ -C H ₂ -C H ₂ -Si- (O-CH ₃ ) ₃ , Si-C H ₂ -CH ₂ -CF ₃ ); 0.21- 0.17 (m, 18H, Si (C H ₃ ) ₂ -CH ₂ -CH ₂ -S-CH ₂ -CH ₂ -CH ₂ -Si- (O-CH ₃ ) ₃ ) ppm.
²⁹ Si-HMR (in CDCl ₃ , 80MHz): δ 11.17, -42.36, -66.25, -68.13, -69.31 ppm.

Example 2
To a solution of tris (dimethylvinylsiloxy) heptatrifluoropropyl incomplete POSS (0.199 g, 0.160 mmol) in tetrahydrofuran (THF) (0.89 ml), vinyltrimethoxysilane (0.077 ml, 0.719 mmol) and 1, 3-Divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex xylene solution (0.1 M) (0.015 ml, 1.60 × 10 ⁻³ mmol) was added and reacted at 50 ° C. for 6 hours. After completion of the reaction, volatile components were distilled off under reduced pressure. The obtained residue was purified by HPLC to obtain a colorless liquid product 2 in a yield of 78% (FIGS. 3 and 4).

¹ H-HMR (in CDCl ₃ , 400MHz): δ 3.58-3.57 (m, 27H, Si (CH ₃ ) ₂ -CH ₂ -CH ₂ -Si- (OC H ₃ ) ₃ ); 2.13-2.06, (m , 14H, Si-CH ₂ -C H ₂ -CF ₃ ); 1.08-0.79 (m, 14H, Si-C H ₂ -CH ₂ -CF ₃ ); 0.62-0.52 (m, 12H, Si (CH ₃ ) ₂ -C H ₂ -C H ₂ -Si- (O-CH ₃ ) ₃ ); 0.19-0.14 (m, 18H, Si (C H ₃ ) ₂ -CH ₂ -CH ₂ -Si- (O-CH ₃ ) ₃ ) ppm.
²⁹ Si-HMR (in CDCl ₃ , 80MHz): δ 13.05, 13.01, 12.43, -66.28, -68.26, -69.49, -69.55, -69.61 ppm.

Example 3 Measurement of transmittance of fluorine-containing silsesquioxane polymer H ₂ 0 (0.02 ml) and tetrahydrofuran (0.2 ml) were added to the silsesquioxane (0.20 g, 0.059 mmol) of Example 2, and 1 drop of 1M aqueous hydrochloric acid solution was added. After the addition, the mixture was vigorously stirred at room temperature for 1 hour. The obtained sol was placed in a polypropylene beaker, allowed to stand overnight at room temperature, and then subjected to a condensation reaction at 70 ° C. for 3 hours. As a result, an optically transparent glass body was obtained (FIG. 5).

  While the embodiments and examples of the present invention have been specifically described above, the present invention is not limited to the above-described embodiments, and various modifications based on the technical idea of the present invention are possible.

  For example, the configurations, methods, processes, shapes, materials, numerical values, and the like given in the above-described embodiments and examples are merely examples, and different configurations, methods, processes, shapes, materials, numerical values, and the like are necessary as necessary. May be used.

  The configurations, methods, processes, shapes, materials, numerical values, and the like of the above-described embodiments can be combined with each other without departing from the gist of the present invention.

  The silsesquioxane according to the present invention can obtain silsesquioxane according to the purpose, including fluorine-containing silsesquioxane. In particular, when the silsesquioxane of the present invention has fluorine, since it has a structure in which a large number of fluorine-containing groups are introduced at high density into a rigid and bulky dice-like inorganic skeleton, even if it is a short perfluoroalkyl chain Molecular mobility is suppressed, and excellent weather resistance, water repellency, oil repellency, non-tackiness and antifouling properties are exhibited. For this reason, the silsesquioxane according to the present invention has, for example, a coating with excellent scratch resistance and / or heat resistance, a surface modification excellent in weather resistance, water repellency, oil repellency, non-tackiness, and / or antifouling properties. Low refractive index UV transparent and / or visible light transparent optically transparent material (glass substitute material) excellent in heat resistance, transparent silsesquioxane material having low refractive index, water repellent material (especially High water vapor barrier materials), oil repellent materials, antifouling agents, electronic materials such as low dielectric constant interlayer insulation films, optical communication materials such as clad materials for polymer optical fibers, and optical members such as antireflection films are also assumed. The

Claims (4)

Silsesquioxane represented by the formula (I).
(In the formula, each R ¹ independently represents a hydrocarbon group or a fluorinated alkyl,
Each Y independently represents — (CH ₂ ) _m —Si (OR ² ) ₃ ,
_{- (CH 2) m -S- (} CH 2) n -Si (OR 2) 3,
_{- (CH 2) m -S- (} CH 2) n -Si (OR 2) 2 CH 3 , or -Si-Z (CH _{3), 2,}
m and n are each independently an integer from 1 to 4,
Each R ² is independently methyl or ethyl;
Z is — (CH ₂ ) _p —Si (OR) ₃ ,
_{- (CH 2) p -S- (} CH 2) q -Si (OR 3) 3,
_{- (CH 2) p -S- (} CH 2) q -Si (OR 3) 2 CH 3,
_{- (CH 2) s -O-} CO (NH) - (CH 2) t -Si (OR 3) 3 or,
_{- (CH 2) s -O-} CO (NH) - (CH 2) t -Si (OR 3) a ₂ CH _3,
p and q are each independently an integer from 1 to 4,
s and t are each independently an integer from 1 to 6;
Each R ³ is independently methyl or ethyl. ) Each R ¹ is independently
And
Each Y independently represents — (CH ₂ ) _m —Si (OR ² ) ₃ ,
_{- (CH 2) m -S- (} CH 2) n -Si (OR 2) 3, or _{- (CH 2) m -S- (} CH 2) n -Si (OR 2) a ₂ CH _3,
m and n are each independently an integer from 1 to 4,
The silsesquioxane according to claim 1, wherein each R ² is independently methyl or ethyl. The silsesquioxane of Claim 1 represented by a formula (II).
(In the formula, each R ¹ independently represents a hydrocarbon group or a fluorinated alkyl,
Each Z is, _{independently, - (CH 2) p -Si} (OR 3) 3,
_{- (CH 2) p -S- (} CH 2) q -Si (OR 3) 3,
_{- (CH 2) p -S- (} CH 2) q -Si (OR 3) 2 CH 3,
_{- (CH 2) s -O-} CO (NH) - (CH 2) t -Si (OR 3) 3 or,
_{- (CH 2) s -O-} CO (NH) - (CH 2) t -Si (OR 3) a ₂ CH _3,
Where p and q are each independently an integer from 1 to 4,
s and t are each independently an integer from 1 to 6;
Each R ³ is independently methyl or ethyl. )   The optically transparent material containing the polymer of the silsesquioxane in any one of Claims 1-3.