JP6884366B2 - Fluorine-containing silsesquioxane, method for producing fluorine-containing silsesquioxane, and polymer - Google Patents

Description

The present invention relates to a fluorine-containing silsesquioxane, a method for producing the fluorine-containing silsesquioxane, and a polymer containing a structural unit composed of the fluorine-containing silsesquioxane.

Fluoroalkyl compounds are chemically stable, have excellent heat resistance, chemical resistance, weather resistance, and acid resistance, and have excellent intermolecular cohesive force and low surface free energy, resulting in excellent water repellency, oil repellency, and non-acidity. Adhesiveness and antifouling property can be obtained. On the other hand, cage-type silsesquioxane (POSS) is attracting attention as a nanobuilding block made of a hybrid material of organic and inorganic materials. Among them, the fluorine-containing cage-type octacil sesquioxane compound (T ₈ ) has a structure in which a large number of fluorine-containing groups are introduced at high density into a rigid and bulky cube-shaped inorganic skeleton, and thus is short perfluoroalkyl. A material can be obtained in which the molecular motility is suppressed even in the case of a chain, and the above-mentioned properties of the fluoroalkyl compound are further emphasized. Applications are being developed to further introduce polymerizable functional groups into fluorine-containing cage-type silsesquioxane compounds.

However, when a polymerizable functional group is introduced into a fluorine-containing cage-type silsesquioxane compound, a monofunctional group (Patent Documents 1 to 3) or a trifunctional group (Patent Documents 1 to 3) is used for one fluorine-containing cage-type silsesquioxane compound. It was limited to Patent Documents 4 and 5).

In the case of a monofunctional group, due to the high crystallinity of the fluorine-containing cage-type silsesquioxane compound, amorphous optical containing the fluorine-containing cage-type silsesquioxane compound at a high density when polymerized. It is difficult to obtain a transparent material.

Further, in the case of a trifunctional group, it is difficult to completely control the polymer structure at the molecular level because a network-like network polymer is formed by polymerization. Further, such a polymer is a thermosetting resin, which is insoluble in an organic solvent and cannot be recovered.

Finer control of the molecular structure of the polymer is required in order to further improve the physical properties and functions.

JP 2012-1724 JP 2012-86419 JP 2014-65706 JP 2006-298947 JP 2014-152246

One object of the present invention is to obtain a fluorine-containing silsesquioxane in which the structure of a fluorine-containing silsesquioxane polymer can be easily controlled, a method for producing the fluorine-containing silsesquioxane, and the fluorine-containing silsesquioxane. It is an object of the present invention to provide a polymer containing as a constituent unit.

Another object of the present invention is to provide a bifunctional fluorine-containing cage-type silsesquioxane polymer that is soluble in an organic solvent.

The present inventors have succeeded in developing a bifunctional fluorine-containing silsesquioxane monomer, which is a new functional material, in order to achieve the above object. The polymer obtained by polymerizing such a monomer has a clear molecular structure and can be soluble in an organic solvent.

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

(In the formula, Rf independently represents alkyl fluoride,
X and Y are the same or different, hydrogen, hydroxyl group, alkenyl, or halogen, alkoxy, phenoxy, polyalkyleneoxy, -COOH, acetyl, 2-oxapropane-1,3-dioil, alkoxycarbonyl, alkenyloxycarbonyl, Oxylanyl, 3,4-epoxycyclohexyl, oxetanyl, oxetanylene, -NH-, -NH ₂ , -CN, -NCO, alkoxy, alkynyl, cycloalkoxy, acryloyloxy, methacryloyloxy, urethane acryloyl, urethane methacryloyl, -SH, alkylene It shows any group from the hydrogen to the −SH or a polymerizable functional group via. )
[2] A base is added to a solution containing a fluorine-containing silsesquioxane represented by the formula (II) to produce a fluorine-containing silsesquioxane represented by the formula (III), and

A formula (III) comprising reacting the fluorine-containing silsesquioxane represented by the formula (III) with a reactive silane having a polymerizable functional group to produce the fluorine-containing silsesquioxane represented by the formula (I). A method for producing a fluorine-containing silsesquioxane represented by I).

(In the formula, Rf independently represents alkyl fluoride,
X and Y are the same or different, hydrogen, hydroxyl group, alkenyl, or halogen, alkoxy, phenoxy, polyalkyleneoxy, -COOH, acetyl, 2-oxapropane-1,3-dioil, alkoxycarbonyl, alkenyloxycarbonyl, Oxylanyl, 3,4-epoxycyclohexyl, oxetanyl, oxetanylene, -NH-, -NH ₂ , -CN, -NCO, alkoxy, alkynyl, cycloalkoxy, acryloyloxy, methacryloyloxy, urethane acryloyl, urethane methacryloyl, -SH or alkylene It shows any group from the hydrogen to the −SH or a polymerizable functional group via. )
[3] A polymer containing a structural unit composed of fluorine-containing silsesquioxane represented by the formula (IV).

(In the formula, Rf independently represents alkyl fluoride,
Z ^{is, -W 1 SiR 1 R 2 -O-} (SiR 3 R 4 -O) m -SiW 2 - or ^{-R 5 -S-R 6 -S-} R 7 - and is,
In the formula, W ¹ and W ² are the same or different alkylene, R ¹ and R ² are the same or different alkyl or aryl, R ³ and R ⁴ are the same or different alkyl or aryl, m is 0 or more. It is an integer, R ⁵ and R ⁷ represent the same or different alkylene, and R ⁶ represents alkylene or aryl. )
[4] Optical containing a fluorine-containing silsesquioxane polymer obtained by polymerizing a fluorine-containing silsesquioxane monomer via a polymerizable functional group bonded to two Sis having a diagonal positional relationship. Transparent material.

According to the bifunctional fluorine-containing silsesquioxane monomer according to the present invention, a fluorine-containing silsesquioxane polymer having a clearly controlled molecular structure can be produced.

¹ H-NMR spectrum of POSS7F1A (Compound 2) in acetone-d6. ¹ H-NMR spectrum of POSS6F1A (Compound 3) in acetone-d6. ¹ H-NMR spectrum of POSS6F2A (Compound 4) in acetone-d6. ²⁹ Si-NMR data of compound 2, compound 3, compound 4 in acetone-d6. (A) MS analysis of POSS6F2A (Compound 4) and silver and (b) stimulation patterns. GPC traces of compound 4, compound 5a, compound 5b, and compound 5b further dissolved in THF using tetrahydrofuran as the eluent. Photograph of a glass-like transparent material produced from the fluorine-containing silsesquioxane polymer of the example. The graph of the transmittance of the fluorine-containing silsesquioxane polymer of this invention.

The fluorine-containing silsesquioxane of the present invention is represented by the following formula (I). The Rf group is bonded to the six Sis of the squirrel-cage octasilsesquioxane (T ₈ ), and the X and Y functional groups are bonded to the remaining two Sis. The two Sis to which X and Y are bonded are in a diagonal positional relationship with the squirrel-cage octacil sesquioxane.

In the formula, each Rf independently represents an alkyl fluoride.

X and Y are the same or different, hydrogen, hydroxyl group, alkenyl, or halogen, alkoxy, phenoxy, polyalkyleneoxy, -COOH, acetyl, 2-oxapropane-1,3-dioil, alkoxycarbonyl, alkenyloxycarbonyl, Oxylanyl, 3,4-epoxycyclohexyl, oxetanyl, oxetanylene, -NH-, -NH ₂ , -CN, -NCO, alkoxy, alkynyl, cycloalkoxy, acryloyloxy, methacryloyloxy, urethane acryloyl, urethane methacryloyl, -SH, alkylene It shows any group from the hydrogen to the −SH or a polymerizable functional group via.

When X and Y are alkenyl, alkoxy, polyalkyleneoxy, alkoxycarbonyl, alkenyloxycarbonyl, alkoxycarbonyl, alkenyloxycarbonyl, alkenyl, alkynyl, cycloalkenyl, the number of carbon atoms is preferably 1 to 10, preferably 1 to 6. Is more preferable (3 or more in the case of cycloalkoxy). The halogen is preferably chlorine, bromine or iodine. When any of the groups from hydrogen to −SH is attached via −alkylene, the alkylene bonded to Si is not particularly limited, but the number of carbon atoms is preferably 1 to 10, and is preferably 1 to 6. Is more preferable.

X and Y are preferably 1) hydrogen via alkylene, hydroxyl group via alkylene, alkoxy via alkylene, halogen via alkylene, -NH via alkylene, -NH ₂ via alkylene, alkylene. -SH or polymerizable functional group via alkylene; 2) alkoxy via alkylene, phenoxy via alkylene, acetyl via alkylene, acryloyloxy via alkylene, or methacryloyloxy via alkylene; or 3) Hydrogen, hydroxyl group, alkenyl, or halogen, alkoxy, phenoxy, polyalkyleneoxy, -COOH, acetyl, 2-oxapropane-1,3-dioil, alkoxycarbonyl, alkoxycarbonyl, oxylanyl, 3,4-epoxycyclohexyl, oxetanyl , Oxetanilen, -NH-, -NH ₂ , -CN, -NCO, Alkoxy, Alkinyl, Cycloalkoxy, Acryloyloxy, Methacryloyloxy, Urethaneacryloyl, Urethanemethacryloyl, -SH; Polyalkyleneoxy via alkylene, via alkylene 2-oxapropane-1,3-dioil, alkoxycarbonyl via alkylene, alkenyloxycarbonyl via alkylene, oxylanyl via alkylene, 3,4-epoxycyclohexyl via alkylene, oxetanyl via alkylene, Oxetanirene via alkylene, -CN via alkylene, -NCO via alkylene, alkoxy via alkylene, alkoxyl via alkylene, cycloalkoxy via alkylene, urethane acryloyl via alkylene, or via alkylene. Urethane methacryloyl.

The polymerizable functional groups include methacryloyl, acryloyl, allyl, styryl, α-methylstyryl, vinyl, vinyl ether, vinyl ester, acrylamide, methacrylamide, N-vinylamide, maleic acid ester, fumaric acid ester, N-substituted maleimide and the like. included.

The carbon number of Rf is preferably 1 to 10 and more preferably 1 to 6 in consideration of solubility in a solvent. Further, Rf may be a straight chain or a branched chain. Examples of the alkyl of Rf include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, heptyl and the like. The number of fluorines in Rf may be 1, 2, 3, 4, 5, or more. As an example of linear Rf, −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 CF as an example of branch chain Rf ( 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 ) ₂ CF ₃ etc. ..
Preferably, Rf is a perfluoroalkyl (all functional groups attached to the carbon of Rf are fluorine). -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 ) 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 (CF 3) 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.

The present inventors use the fluorine-containing silsesquioxane of the above formula (I) as a diagonal of the Si of a monofunctional fluorine-containing silsesquioxane in which a functional group X is bonded to one Si. A step of cleaving the Si—O bond of Si in the positional relationship of (1st step, hereinafter referred to as a corner opening reaction) and a 1st step of opening a corner of the cage-shaped structure of fluorine-containing silsesquioxane. A step of reacting a reactive silane with the fluorine-containing silsesquioxane opened in 1 and adding Si in a form having a polymerizable functional group to close the above-mentioned corner of the cage-shaped structure of the fluorine-containing silsesquioxane (No. 1). It was successfully manufactured by two steps, hereinafter referred to as a corner capping reaction). As the monofunctional fluorine-containing silsesquioxane, a known one may be used, or a monofunctional fluorine-containing silsesquioxane may be prepared by adding a monofunctional group to the fluorine-containing silsesquioxane having no functional group by a known technique. Good.

The method for producing a fluorine-containing silsesquioxane represented by the formula (I) of the present invention is:
A base is added to a solution containing a fluorine-containing silsesquioxane represented by the formula (II) to produce a fluorine-containing silsesquioxane represented by the formula (III) (first step), and

Reacting a fluorine-containing silsesquioxane represented by the above formula (III) with a reactive silane having a polymerizable functional group to produce a fluorine-containing silsesquioxane represented by the following formula (I) (second). Process)
including.

In the formula, Rf independently represents alkyl fluoride,
X and Y are the same or different, hydrogen, hydroxyl group, alkenyl, or halogen, alkoxy, phenoxy, polyalkyleneoxy, -COOH, acetyl, 2-oxapropane-1,3-dioil, alkoxycarbonyl, alkenyloxycarbonyl, Oxylanyl, 3,4-epoxycyclohexyl, oxetanyl, oxetanylene, -NH-, -NH ₂ , -CN, -NCO, alkoxy, alkynyl, cycloalkoxy, acryloyloxy, methacryloyloxy, urethane acryloyl, urethane methacryloyl, -SH, alkylene It shows any group from the hydrogen to the −SH or a polymerizable functional group via.

The explanation of Rf, X, and Y is as described above for the fluorine-containing silsesquioxane represented by the formula (I).

In the first step, the fluorine-containing silsesquioxane is dissolved in an organic solvent to prepare a solution containing the fluorine-containing silsesquioxane. Examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, and the like. Examples thereof include ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichlorethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane and the like.

Further, in order to promote the corner opening reaction, a base is added to a solution containing fluorine-containing silsesquioxane to cause the reaction. Tetraalkylammonium is preferable as such a base, and tetramethylammonium and tetraethylammonium are particularly mentioned. After the reaction, the salt is removed by filtration, and the organic solvent is removed by a known means such as vacuum distillation to obtain a fluorine-containing silsesquioxane represented by the formula (III).

The reactive silane having a polymerizable functional group in the second step has a polymerizable functional group and a reactive group. Examples of polymerizable functional groups include methacryloyl, acryloyl, allyl, styryl, α-methylstyryl, vinyl, vinyl ether, vinyl ester, acrylamide, methacrylamide, N-vinylamide, maleic acid ester, fumaric acid ester, N-substituted maleimide and the like. Is included. Examples of reactive groups are a trichlorosilyl group and a trialkoxysilyl group (alkoxy groups have 1 to 5 carbon atoms).

The reactive silane having a polymerizable functional group is, for example, a general formula: A ¹¹ −A ²¹ −Si (A ³¹ ) ₃ [in the formula, A ¹¹ is a polymerizable functional group, and A ²¹ is a direct bond or the number of carbon atoms. It is an alkyl group of 1 to 20 (for example, 1 to 10), and A ³¹ is a halogen atom (for example, a chlorine atom and a bromine atom) or an alkoxy group (the alkoxy group has 1 to 6 carbon atoms). ] Is a compound indicated by.

According to the above production method, a bifunctional fluorine-containing silsesquioxane in which a functional group is bonded to two Sis having a diagonal positional relationship can be produced.

The polymer of the present invention contains a structural unit composed of a fluorine-containing silsesquioxane represented by the following formula (IV). The structural unit composed of the fluorine-containing silsesquioxane represented by the following formula (IV) can be derived from the fluorine-containing silsesquioxane monomer represented by the formula (I) of the present invention, and the single amount thereof. A polymer can be produced by polymerizing the body under a catalyst such as a platinum catalyst.

(In the formula, Rf independently represents alkyl fluoride,
Z ^{is, -W 1 SiR 1 R 2 -O-} (SiR 3 R 4 -O) m -SiW 2 - or ^{-R 5 -S-R 6 -S-} R 7 - and is,
In the formula, W ¹ and W ² are the same or different alkylene, R ¹ and R ² are the same or different alkyl or aryl, R ³ and R ⁴ are the same or different alkyl or aryl, m is 0 or more. It is an integer, R ⁵ and R ⁷ represent the same or different alkylene, and R ⁶ represents alkylene or aryl. )
W ¹ and W ² may be methylene, ethylene, propylene, n-butylene, isobutylene, hexylene, heptene, octylene, dodecylene and the like. The carbon number of W ¹ and W ² is preferably 1 to 10, and more preferably 1 to 6.

When R ¹ and R ² are alkyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, hexyl, octyl, decyl, dodecyl and the like can be mentioned, and R ¹ and R ² have 1 to 10 carbon atoms. It is preferably 1 to 6, and more preferably 1 to 6. When R ¹ and R ² are aryl, aryl includes phenyl, biphenyl, anthryl, pyrenyl, fluorenyl, naphthyl and the like. In ^{the case of alkyl or aryl, R 1} and R ² may further have a substituent such as a methyl group.

When R ³ and R ⁴ are alkyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, hexyl, octyl, decyl, dodecyl and the like can be mentioned, and R ³ and R ⁴ have 1 to 10 carbon atoms. It is preferably 1 to 6, and more preferably 1 to 6. When R ³ and R ⁴ are aryl, aryl includes phenyl, biphenyl, anthryl, pyrenyl, fluorenyl, naphthyl and the like. In ^{the case of alkyl or aryl, R 3} and R ⁴² may further have a substituent such as a methyl group.

The number of m is not particularly limited, but is preferably 0 or more and 20 or less, and more preferably 0 or more and 10 or less.

R ⁵ and R ⁷ may be methylene, ethylene, propylene, n-butylene, isobutylene, hexylene, heptene, octylene, dodecylene and the like. The carbon number of R ⁵ and R ⁷ is preferably 1 to 10, and more preferably 1 to 6.

When R ⁶ is alkyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, hexyl, octyl, decyl, dodecyl and the like can be mentioned, and R ⁶ preferably has 1 to 10 carbon atoms, preferably 1 to 6. More preferably. When R ³ and R ⁴ are aryl, aryl includes phenyl, biphenyl, anthryl, pyrenyl, fluorenyl, naphthyl and the like. In ^{the case of alkyl or aryl, R 6} may further have a substituent such as a methyl group.

The weight average molecular weight of the obtained polymer is not particularly limited, but is preferably about 500 to about 1,000,000, and more preferably about 1,000 to 100,000. The weight average molecular weight can be determined by GPC analysis.

The polymer containing the structural unit composed of the fluorine-containing silsesquioxane represented by the formula (IV) of the present invention is a heavy body composed of only one kind of bifunctional fluorine-containing silsesquioxane monomer of the present invention. It can also be a copolymer of the fluorine-containing silsesquioxane monomers of the present invention having different polymerizable functional groups, or the fluorine-containing silsesquioxane monomers of the present invention. And a copolymer of a fluorine-free silsesquioxane monomer, or the common weight of the fluorine-containing silsesquioxane monomer of the present invention and another general monomer. It can also be combined. In the case of a copolymer of fluorine-containing silsesquioxane having different polymerizable functional groups, any fluorine-containing silsesquioxane may be the bifunctional fluorine-containing silsesquioxane of the present invention. It may be a copolymer of a bifunctional fluorine-containing silsesquioxane monomer and a monofunctional fluorine-containing silsesquioxane monomer, or a bifunctional fluorine-containing silsesquioxane. It may be a copolymer of a monomer and a trifunctional fluorine-containing silsesquioxane monomer. Furthermore, a known polymer containing a structural unit composed of fluorine-containing silsesquioxane represented by the formula (IV) of the present invention can be polymerized with a polymer containing a structural unit composed of fluorine-containing silsesquioxane. It may further contain structural units derived from polymerizable functional groups.

According to the present invention, since the polymer is formed by using the bifunctional fluorine-containing silsesquioxane monomer, it is easy to control the molecular structure of the polymer.

The present invention also includes a fluorine-containing silsesquioxane polymer obtained by polymerizing a fluorine-containing silsesquioxane monomer via a polymerizable functional group bonded to two Sis having a diagonal positional relationship. Includes optically transparent material. Examples of such polymerizable functional groups include the polymerizable functional groups described with respect to X and Y or Z.

The fluorine-containing silsesquioxane polymer is a heavy body composed of only one of the above-mentioned bifunctional fluorine-containing silsesquioxane monomers of the present invention, and contains fluorine of the present invention having different polymerizable functional groups. A copolymer of silsesquioxane monomers, a copolymer of the fluorine-containing silsesquioxane monomer of the present invention and a fluorine-free silsesquioxane monomer, and a fluorine-containing silsesqui of the present invention. It contains a copolymer of an oxane monomer and another common monomer.

Fluorine-containing silsesquioxane glass, which is an optically transparent material, can be obtained by heat-treating the above-mentioned polymer under vacuum or reduced pressure for a certain period of time at a certain temperature. The heat treatment time is not limited, but is, for example, about 1 hour to 1 week. The temperature of the heat treatment is not limited, but is, for example, 100 to 200 ° C.

The refractive index of the optically transparent material of the present invention is not limited, but is preferably 1.2 to 1.5, and 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 in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 Production of allyl hepta (3,3,3-trifluoropropyl) (POSS7F1A) (Compound 2) POSS7F3Na (Compound 1) synthesized with reference to Chem. Lett., 2014, 43, 1532 under a nitrogen atmosphere. 4.0 g, 3.52 mmol) and allyltrichlorosilane (0.76 ml, 5.28 mmol) are dissolved in THF (60 ml), soaked in an ice bath, then triethylamine (0.49 ml, 3.52 mmol) is added, and the mixture is placed in an ice bath for 1 hour. The mixture was stirred at room temperature for 3 hours. After the reaction, the salt was removed by filtration, the solvent was distilled off under reduced pressure, and the mixture was washed with MeOH to obtain Compound 2 in a yield of 52%. ¹ H-NMR and ²⁹ Si-NMR were measured for Compound 2 (Figs. 1 and 4).
^{1 1} H NMR (Acetone-D6, 400 MHz): 5.87-5.80 (m, 1H, Si-CH ₂ -CH-CH ₂ ), 5.06-4.94 (m, 2H, Si-CH ₂ -CH-CH ₂ ), 2.34-2.29 (m, 14H, Si-CH ₂ -CH ₂ -CF ₃ ), 1.79-1.77 (w, 2H, Si-CH ₂ -CH-CH ₂ ), 1.03-0.99 (m, 14H, Si-CH ₂ -CH ₂ -CF ₃ ) ppm.
²⁹ Si NMR (Acetone-D6, 79 MHz): -70.18 (-CH ₂ -SiO _1.5 ), -67.51, -67.48 and -67.33 (CF ₃ -CH ₂ -CH ₂ -SiO _1.5 ) ppm.

Example 2 Production of allylhexa (3,3,3-trifluoropropyl) (POSS6F1A) (Compound 3) Compound 2 (0.50 g, 0.44 mmol) is dissolved in ethyl acetate (7.8 mL) and equimolar to compound 1. A 25% aqueous solution of tetramethylammonium (TMAOH) (0.19 ml, 0.44 mmol) was added, and the mixture was stirred at room temperature for 4 hours. After the stirring was completed, 1M-HCl was added dropwise until it could be confirmed by pH test paper that it was neutral. Then a small amount of magnesium sulfate was added. After removing magnesium sulfate by filtration, the solvent was distilled off under reduced pressure. Methanol was added to the obtained solid and removed by filtration as an insoluble component, the filtrate was evaporated under reduced pressure, the solvent was distilled off, and the precipitated viscous solid was dried under reduced pressure. 0.30 g of a product (Compound 3) in which the diagonal of Compound 2 was hydrolyzed was considered to be the main component was obtained. The yield was 66%. ^{Measurements of 1} H- and ²⁹ Si-NMR were carried out for Compound 3 (Figs. 2 and 4). ^{From 29} Si-NMR measurement, a signal corresponding to Si-OH was observed at -59 ppm.
¹ H-NMR (Acetone-d6, 400 MHz): δ5.88-5.83 (m, 1H, Si-CH ₂ -CH-CH ₂ ), 5.05-4.97 (m, 2H, Si-CH ₂ -CH-CH) ₂ ), 2.32-2.31 (m, 12H, Si-CH ₂ -CH ₂ -CF ₃ ), 1.81-1.78 (w, 2H, Si-CH ₂ -CH-CH ₂ ), 1.02-1.01 (m, 12H, Si-CH ₂ -CH ₂ -CF ₃ ) ppm.
²⁹ Si NMR (Acetone-d6, 79 MHz): -71.55, -67.25 and -59.23 ppm.

Example 3. Synthesis of bisallylhexa (3,3,3-trifluoropropyl) (POSS6F2A) Under a nitrogen atmosphere, compound 3 (0.30 g, 0.29 mmol) and allyltrichlorosilane (0.05 ml, 0.35 mmol)) were added in THF (5 ml). ), Soaked in an ice bath, triethylamine (0.04 ml, 0.29 mmol) was added, and the mixture was stirred in an ice bath for 1 hour and at room temperature for 3 hours. After the reaction, the salt was removed by filtration, the solvent was distilled off under reduced pressure, and the mixture was washed with MeOH to obtain 0.16 g of the product (Compound 4). The yield was 52%. Compound 4 ^{was confirmed by 1} H-NMR, ²⁹ Si-NMR measurement and high-resolution mass spectrometric measurement (Figs. 3, 4, and 5). ²⁹ Two signals were observed in the Si-NMR measurement, which supported the structure of compound 4 in which the polymerizable functional group was modified at the two diagonal vertices (Fig. 4).
^{1 1} H NMR (Acetone-d6, 400 MHz): 5.85-5.83 (m, 2H, Si-CH ₂ -CH-CH ₂ ), 4.97-4.95 (m, 4H, Si-CH ₂ -CH-CH ₂ ), 2.34-2.28 (m, 12H, Si-CH ₂ -CH ₂ -CF ₃ ), 1.79-1.63 (w, 4H, Si-CH ₂ -CH-CH ₂ ), 1.03-1.01 (m, 12H, Si-CH) ₂ -CH ₂ -CF ₃ ) ppm.
²⁹ Si NMR (Acetone-d6, 79 MHz): -69.75 and -98.93 ppm.
HR-FAB-MS (m / z): calcd for C ₂₈ H ₆₀ O ₁₂ Si ₈ [M + Ag] ⁺ , 1186.8959; obs, 1186.9088.

Example 4. Polymer Synthesis Compound 4 (0.20 g, 0.24 mmol) and 1,1,3,3-tetramethyldisiloxane (0.043 ml, 0.24 mmol) were dissolved in THF (0.83 ml) and Pt (dvs) (0.1 M). Polymerization was carried out by adding in xylene, 0.01 ml, 1.0 × 10-3 mmol) and stirring at 50 ° C. for 24 hours (Scheme 4). A polymer 5a (m = 0) was obtained by removing low molecular weight components from the obtained polymerization solution using a preparative GPC. GPC measurement of polymer 5a revealed that the polymers had a number average molecular weight (Mn) and a molecular weight distribution (Mw / Mn) ^{corresponding to 7.7 × 10 3} and 1.45, respectively, in terms of polystyrene (Fig. 6). .. An example in which the polymer 5a is drop-cast onto a glass substrate to form a glass-like transparent material is shown in FIG.

Compound 4 (0.13 g, 0.12 mmol) and polydimethylsiloxane (Mn to 580) (0.076 ml, 0.12 mmol) were dissolved in THF (1.2 ml) and Pt (dvs) (0.1 M in xylene, 0.012 ml, 1.2 ×). 10-3 mmol) was added and the mixture was stirred at 50 ° C. for 12 hours for polymerization (Scheme 4). THF was added to the polymer 5b (m = 6) obtained by distilling off the solvent under reduced pressure, and the GPC measurement of the soluble component was performed. As a result, the number average molecular weight (Mn) and the molecular weight distribution in terms of polystyrene were measured. It was found that (Mw / Mn) was ^{a polymer corresponding to 3.3 × 10 3} and 2.68, respectively (Fig. 6). Further, the polymer 5b to which THF was added was continuously stirred at room temperature for 1 week, and almost all of the polymer was dissolved. GPC measurement of the THF solution revealed that the polymers had a number average molecular weight (Mn) and a molecular weight distribution (Mw / Mn) ^{corresponding to 1.6 × 10 4} and 1.92, respectively (Fig. 6).

Example 5. Measurement of transmittance of fluorine-containing silsesquioxane polymer A THF solution (10 mg / mL) of polymers 5a and 5b is spin-coated on a glass substrate, and only the glass substrate is used as the background, and the polymer is transmitted by an ultraviolet-visible spectrophotometer. The rate was measured (Fig. 8). As a result, it was found that the transmittance was wavelength-dependent.
Example 6. Refractive index measurement of fluorine-containing silsesquioxane polymer A sample was prepared by spin-coating a THF solution of polymers 5a and 5b on a silicon substrate, and the film thickness and refractive index were measured with a spectroscopic ellipsometer (Table 1). ).

Although 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, etc. given in the above-described embodiments and examples are merely examples, and if necessary, different configurations, methods, processes, shapes, materials, numerical values, etc. May be used.

In addition, the configurations, methods, processes, shapes, materials, numerical values, etc. of the above-described embodiments can be combined with each other as long as they do not deviate from the gist of the present invention.

The fluorine-containing silsesquioxane polymer obtained by polymerizing the bifunctional hexatrifluoropropyl T8 monomer according to the present invention has a clear molecular structure. Since the molecular structure of the fluorine-containing silsesquioxane polymer can be changed in a controlled manner, it is possible to obtain a fluorine-containing silsesquioxane polymer according to the purpose. Therefore, for example, it is expected that an optically transparent material (glass substitute) having excellent heat resistance and low refractive index and / or visible light transmission will be used. In addition, silsesquioxane transparent materials having a low refractive index, water-repellent materials (particularly high water vapor barrier materials), oil-repellent materials, antifouling agents, electronic materials such as low dielectric constant interlayer insulating films, and clad materials for polymer optical fibers. It is also expected to be used for optical communication materials such as, and optical members such as antireflection films.

Claims (4)

A polymer having a refractive index in the range of 1.2 to 1.35, which comprises a structural unit composed of fluorine-containing silsesquioxane represented by the formula (IV).

(In the formula, Rf independently represents an alkyl fluoride having 1 to 10 carbon atoms.
Z ^{is, -W 1 SiR 1 R 2 -O-} (SiR 3 R 4 -O) m -SiW 2 - or ^{-R 5 -S-R 6 -S-} R 7 - and is,
In the formula, W ¹ and W ² are the same or different alkylene, R ¹ and R ² are the same or different alkyl or aryl, R ³ and R ⁴ are the same or different alkyl or aryl, m is 0 or more. It is an integer, R ⁵ and R ⁷ represent the same or different alkylene, and R ⁶ represents alkylene or aryl. )
For the manufacture of a polymer according to claim 1, as a monomer of the polymer, the use of fluorine-containing silsesquioxane represented by formula (I).

(In the formula, Rf independently represents an alkyl fluoride having 1 to 10 carbon atoms.
X and Y represent the same or different hydrogen, alkenyl, alkylene-mediated alkenyl, alkylene-mediated halogen, allyl, or vinyl . ) A base is added to a solution containing a fluorine-containing silsesquioxane represented by the formula (II) to produce a fluorine-containing silsesquioxane represented by the formula (III), and

The present invention comprises reacting the fluorine-containing silsesquioxane represented by the formula (III) with a reactive silane having a polymerizable functional group to produce the fluorine-containing silsesquioxane represented by the formula (I).
A method for producing a fluorine-containing silsesquioxane represented by the formula (I), which is a monomer of the polymer according to claim 1.

(In the formula, Rf independently represents an alkyl fluoride having 1 to 10 carbon atoms.
X and Y represent the same or different hydrogen, alkenyl, alkylene-mediated alkenyl, alkylene-mediated halogen, allyl, or vinyl . ) An optically transparent material containing the polymer according to claim 1.

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