JP2009280701A - Organic silica-based material and organic silica based mesoporous material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic silica-based material which excels in light resistance and can absorb light in the range of near-ultraviolet rays to visible rays and has a high quantum yield and an organic silica based porous material. <P>SOLUTION: The organic silica-based material includes a polymer of an organosilane precursor represented by formula (2) and a surface active agent and the organic silica-based porous material includes the polymer of the organosilicon compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an organic silica-based material and an organic silica-based mesoporous material, and more particularly to an organic silica-based material having a tetraarylpyrene skeleton and an organic silica-based mesoporous material.

  Polymers of organosilicon compounds having a mesostructure are organic / inorganic hybrid materials that can be expected to be applied to light emitting materials, photocatalysts, solar cells, and the like, and various polymers of organosilicon compounds have been proposed.

  For example, WO 2007/034861 (Patent Document 1) discloses a crosslinked organosilane having a pyrene skeleton, anthracene skeleton, acridone skeleton, acridine skeleton, quaterphenyl skeleton, oligophenylene vinylene skeleton, or the like. Yes. As described in Patent Document 1, since a mesostructure composed of a crosslinked organosilane having a pyrene skeleton or an acridine skeleton absorbs ultraviolet rays, application to an ultraviolet-responsive photocatalyst can be expected. In addition, a mesostructure composed of a crosslinked organosilane having an anthracene skeleton, an acridone skeleton or a quaterphenyl skeleton absorbs visible light of 400 nm or more, so that it can be expected to be applied to a visible light responsive photocatalyst or solar cell. .

  However, mesostructures composed of these crosslinked organosilanes, particularly mesostructures that absorb visible light, have not been sufficient in terms of light resistance.

On the other hand, Japanese Patent Application Laid-Open No. 2002-63988 (Patent Document 2) discloses tetraphenylpyrene and its similar compounds as organic phosphors contained in a light emitting element. JP-A-2003-234190 (Patent Document 3) and 2006-269670 (Patent Document 4) disclose an organic thin film layer containing a 1,3,6,8-tetraphenylpyrene compound in an organic EL element. Is disclosed. However, these tetraphenylpyrene compounds are contained in light emitting elements and organic thin film layers as low molecular weight compounds.
International Publication No. 2007/034861 Pamphlet JP 2002-63988 A JP 2003-234190 A 2006-269670

  The present invention has been made in view of the above-mentioned problems of the prior art, and has excellent light resistance, can absorb light in the region from near ultraviolet to visible light, and has a high quantum yield. An object of the present invention is to provide a porous material and an organic silica porous body.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have developed an organosilica material containing an organosilicon compound polymer and a surfactant, and an organosilica compound comprising the organosilicon compound polymer. In the porous body, by using a polymer having a tetraarylpyrene skeleton as the polymer of the organosilicon compound, the polymer of the organosilicon compound has a mesostructure, and further, an organosilica-based material and an organosilica The present inventors have found that the porous system has excellent light resistance, can absorb light in the region from near ultraviolet to visible light, and has a high quantum yield, and has completed the present invention.

  That is, the organic silica material of the present invention has the following formula (1):

(In the formula (1), each Ar independently represents one arylene group selected from the group consisting of a phenylene group, a biphenylylene group, and a naphthylene group, and the arylene group may have a substituent, Each independently represents a divalent aliphatic organic group, an alkylene group or a single group comprising at least one group selected from the group consisting of an ether group, a thioether group, a carbonyl group, a carbonate group, an amino group, an amide group and a urethane group. R ^{1 to} R ⁶ each independently represent a substituent selected from the group consisting of an alkyl group, an alkoxy group, an amino group, a nitro group, and a cyano group, a halogen atom, or a hydrogen atom.
A polymer of a mesostructured organosilicon compound having a repeating unit represented by formula (II) and a surfactant.

  The organosilica mesoporous material of the present invention is characterized by comprising a polymer of an organosilicon compound having a repeating unit represented by the formula (1).

In the organic silica material and the organic silica mesoporous material of the present invention, the polymer of the organic silicon compound is one in which Ar in the formula (1) is a phenylene group and R ^{1 to} R ⁶ are hydrogen atoms. Is preferred.

  In addition, in an organic silica-based porous material composed of an organic silica-based material containing a polymer of an organosilicon compound and a surfactant and the polymer of the organosilicon compound, the tetrasilane according to the present invention is used as the polymer of the organosilicon compound. By using a polymer having an arylpyrene skeleton, the organic silica-based material and the organic silica-based porous material have excellent light resistance, can absorb light in the region from near ultraviolet to visible light, and have a high quantum yield. Although the reason for having a rate is not necessarily clear, the present inventors infer as follows. That is, the tetraarylene pyrene skeleton can absorb light in the region from near ultraviolet light to visible light, and the polymer of the organosilicon compound according to the present invention also absorbs light in the region from near ultraviolet light to visible light. It can be absorbed. In addition, the tetraarylene pyrene skeleton according to the present invention has a relatively simple organic group in which a benzene ring, a naphthalene ring or a biphenylylene ring is bonded to a pyrene ring as a basic structural unit. Group decomposition is less likely to occur. Furthermore, since the tetraarylene pyrene skeleton is bulky, even when the polymer of the organosilicon compound according to the present invention is present in a high concentration, the interaction between molecules is suppressed, and excitation energy is not deactivated by light irradiation. It is presumed that a high quantum yield can be obtained.

  On the other hand, in a polymer of an organosilicon compound in which only a benzene ring skeleton or a pyrene ring skeleton is introduced instead of a tetraarylene pyrene skeleton, decomposition of an organic group due to continuous light irradiation is less likely to occur, but a benzene ring or a pyrene ring Since the absorption band of is only in the ultraviolet region, it is difficult to absorb visible light. In addition, if an anthracene skeleton, an oligophenylene vinylene skeleton, an acridone skeleton, etc. are introduced to expand the size of the π-conjugated system of the organic group in the polymer of the organosilicon compound, visible light absorption is possible, but quantum yield Becomes lower. This is presumably because the interaction between molecules becomes stronger due to the expansion of the size of the π-conjugated system of the organic group, and many sites that deactivate the photoexcitation energy are formed by the association of the organic group.

  According to the present invention, it is possible to provide an organic silica-based material and an organic silica-based porous body that have excellent light resistance, can absorb light in the near ultraviolet to visible light region, and have a high quantum yield. It becomes.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  First, the organic silica material of the present invention will be described. The organic silica material of the present invention has the following formula (1):

It contains a polymer of a mesostructured organosilicon compound having a repeating unit represented by the formula (hereinafter referred to as “Si-based polymer”) and a surfactant.

  In the Si-based polymer according to the present invention, Ar in the formula (1) represents one kind of arylene group independently selected from the group consisting of a phenylene group, a biphenylylene group, and a naphthylene group. The arylene group may have a substituent such as an alkyl group, an alkoxy group, an amino group, a nitro group, a cyano group, or a halogen group.

  L in the formula (1) each independently represents a divalent group containing at least one group selected from the group consisting of an ether group, a thioether group, a carbonyl group, a carbonate group, an amino group, an amide group, and a urethane group. An aliphatic organic group, an alkylene group or a single bond is represented. 1-12 are preferable and, as for carbon number of the said alkylene group, 1-6 are more preferable. Of these alkylene groups, a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, and a hexamethylene group are particularly preferable, and an ethylene group, a propylene group, and a butylene group are most preferable. The divalent aliphatic organic group preferably further contains a divalent hydrocarbon group having 1 to 12 carbon atoms (more preferably 1 to 6 carbon atoms). As the divalent hydrocarbon group, An alkylene group is preferred.

R ^{1 to} R ⁶ in the formula (1) each independently represents one kind of substituent selected from the group consisting of an alkyl group, an alkoxy group, an amino group, a nitro group and a cyano group, a halogen atom or a hydrogen atom. To express. 1-12 are preferable and, as for carbon number of the said alkyl group and an alkoxy group, 1-6 are more preferable.

Among such Si-based polymers, Ar in the formula (1) is a phenylene group from the viewpoint of achieving a high quantum yield while suppressing the volume fraction of the hydrophobic organic skeleton relative to the silica skeleton, A Si-based polymer in which R ^{1 to} R ⁶ are hydrogen atoms is particularly preferable.

  The Si-based polymer according to the present invention having the repeating unit represented by the formula (1) is, for example, the following formula (2):

It can form by polymerizing the organosilane precursor represented by these.

Ar in the formula (2), L and ^R 1 to R ⁶ are, Ar in the formula (1) have the same meanings as L and ^R 1 to R ^6. R ⁷ represents a methyl group or an ethyl group, and R ⁸ represents an allyl group which may have a substituent such as a methyl group. Although n is an integer of 0 to 3, n is preferably an integer of 1 to 3 from the viewpoint that the condensation reaction easily proceeds and the structure after condensation is stable.

Among such organosilane precursors, Ar in the formula (2) is a phenylene group from the viewpoint of achieving a high quantum yield while suppressing the volume fraction of the hydrophobic organic skeleton relative to the silica skeleton, A Si-based polymer in which R ^{1 to} R ⁶ are hydrogen atoms is particularly preferable.

  Moreover, in this invention, what copolymerized the organosilane precursor represented by said Formula (2) and another organosilane compound can also be used as said Si type polymer. Examples of the other organic silane compounds include dialkoxysilanes such as dimethoxysilane and diethoxysilane; trialkoxysilanes such as trimethoxysilane and triethoxysilane; and known alkoxysilane compounds such as tetraalkoxysilane such as tetramethoxysilane and tetraethoxysilane. Is mentioned.

  When (co) polymerizing the organosilane precursor and, if necessary, the other organosilane compound (hereinafter collectively referred to as “silane monomer”), the ratio of the organosilane precursor is (co) 10-100 mass% is preferable with respect to 100 mass% of all the silane monomers used for superposition | polymerization, and 50-100 mass% is more preferable. The conditions for the (co) polymerization reaction are not particularly limited, but water or a mixed solvent of water and an organic solvent is used as a solvent, and the silane monomer is hydrolyzed and condensed in the presence of an acid or base catalyst. Preferably. Suitable organic solvents used at this time include alcohol, acetone and the like, and the content of the organic solvent when used as a mixed solvent is preferably about 5 to 99% by weight. Examples of the acid catalyst include mineral acids such as hydrochloric acid, nitric acid, and sulfuric acid, and the solution in the case of using the acid catalyst is preferably acidic with a pH of 6 or less (more preferably 2 to 5). . Furthermore, examples of the base catalyst include sodium hydroxide, ammonium hydroxide, potassium hydroxide, and the like. When the base catalyst is used, the solution has a basic pH of 8 or more (more preferably 9 to 11). Preferably there is.

  The concentration of the silane monomer in such a (co) polymerization step is preferably about 0.0055 to 0.33 mol / L in terms of silicon concentration. Further, various conditions (temperature, time, etc.) in the polymerization step are not particularly limited, and are appropriately selected according to the silane monomer to be used, the target Si-based polymer, and the like. The silane monomer is preferably hydrolyzed and condensed at a temperature of about 1 to 48 hours.

  When the organic silane precursor is (co) polymerized, the silyl group in the formula (2) is usually hydrolyzed to form a silanol group (Si—OH), and a siloxane bond (Si— O-Si) is formed. At this time, even if some of the silanol groups are not converted to siloxane bonds and remain as they are, or the allyl groups bonded to Si remain as they are, the light absorption of the organic silica-based material or organic silica-based porous body Does not affect light resistance and quantum yield.

  The organic silica material of the present invention contains a surfactant in addition to the Si polymer. This surfactant has an effect of suppressing association of organic groups in the Si-based polymer and preventing a decrease in quantum yield due to the association.

  Such a surfactant is usually left as it is without removing the one used when preparing the Si polymer. Further, by carrying out the (co) polymerization in the presence of a surfactant, the Si polymer has a structure (mesostructure) having mesopores having a central pore diameter of 1 to 30 nm in a pore diameter distribution curve. ) Having a mesoporous material.

  The central pore diameter is a curve (pore diameter distribution curve) in which a value (dV / dD) obtained by differentiating the pore volume (V) with respect to the pore diameter (D) is plotted against the pore diameter (D). ) At the maximum peak, and can be determined by the method described below. That is, the mesoporous material is cooled to a liquid nitrogen temperature (−196 ° C.), nitrogen gas is introduced, the adsorption amount is determined by a constant volume method or a gravimetric method, and then the pressure of the introduced nitrogen gas is gradually increased. Then, the adsorption amount of nitrogen gas with respect to each equilibrium pressure is plotted to obtain an adsorption isotherm. Using this adsorption isotherm, a pore size distribution curve can be obtained by a calculation method such as Cranston-Inklay method, Pollimore-Heal method, or BJH method.

Such a mesoporous material preferably contains 60% or more of the total pore volume in a range of ± 40% of the center pore diameter in the pore diameter distribution curve. A mesoporous material satisfying this condition means that the pore diameter is very uniform. The specific surface area of the mesoporous material is not particularly limited, but is preferably 700 m ² / g or more. The specific surface area can be calculated as a BET specific surface area from the adsorption isotherm using the BET isotherm adsorption equation.

  Further, such a mesoporous material preferably has one or more peaks at a diffraction angle corresponding to a d value of 1.5 to 30.5 nm in its X-ray diffraction (XRD) pattern. The X-ray diffraction peak means that a periodic structure having a d value corresponding to the peak angle is present in the sample. Therefore, having one or more peaks at a diffraction angle corresponding to a d value of 1.5 to 30.5 nm indicates that the pores are regularly arranged at intervals of 1.5 to 30.5 nm. means.

  The surfactant used in preparing the mesostructured Si-based polymer according to the present invention is not particularly limited, and may be any of cationic, anionic, and nonionic, specifically, Chloride, bromide, iodide or hydroxide such as alkyltrimethylammonium, alkyltriethylammonium, dialkyldimethylammonium, benzylammonium; fatty acid salt, alkylsulfonate, alkylphosphate, polyethylene oxide nonionic surfactant, Primary alkylamines are listed. These surfactants may be used alone or in combination of two or more.

Among the above surfactants, examples of the polyethylene oxide nonionic surfactant include polyethylene oxide nonionic surfactants each having a hydrocarbon group as a hydrophobic component and polyethylene oxide as a hydrophilic portion. Such surfactants, for example, the general formula _{C n H 2n + 1 (OCH} 2 CH 2) expressed in m OH, n is 10 to 30, m can be preferably used those which are 1 to 30. As such a surfactant, an ester of a fatty acid such as oleic acid, lauric acid, stearic acid, and palmitic acid and sorbitan, or a compound obtained by adding polyethylene oxide to these esters can also be used.

Further, as such a surfactant, a triblock copolymer type polyalkylene oxide may be used. Examples of such surfactants include those composed of polyethylene oxide (EO) and polypropylene oxide (PO) and represented by the general formula (EO) _x (PO) _y (EO) _x . x and y represent the number of repetitions of EO and PO, respectively, x is preferably 5 to 110, y is preferably 15 to 70, x is preferably 13 to 106, and y is more preferably 29 to 70. Examples of the triblock copolymer include (EO) ₁₉ (PO) ₂₉ (EO) ₁₉ , (EO) ₁₃ (PO) ₇₀ (EO) ₁₃ , (EO) ₅ (PO) ₇₀ (EO) ₅ , (EO). ₁₃ (PO) ₃₀ (EO) ₁₃ , (EO) ₂₀ (PO) ₃₀ (EO) ₂₀ , (EO) ₂₆ (PO) ₃₉ (EO) ₂₆ , (EO) ₁₇ (PO) ₅₆ (EO) ₁₇ , ( EO) ₁₇ (PO) ₅₈ (EO) ₁₇ , (EO) ₂₀ (PO) ₇₀ (EO) ₂₀ , (EO) ₈₀ (PO) ₃₀ (EO) ₈₀ , (EO) ₁₀₆ (PO) ₇₀ (EO) ₁₀₆ , (EO) ₁₀₀ (PO) ₃₉ (EO) ₁₀₀ , (EO) ₁₉ (PO) ₃₃ (EO) ₁₉ , (EO) ₂₆ (PO) ₃₆ (EO) ₂₆ . These triblock copolymers are available from BASF, Aldrich, etc., and triblock copolymers having desired x and y values can be obtained at a small scale production level.

Also, a star diblock copolymer in which two polyethylene oxide (EO) chains-polypropylene oxide (PO) chains are bonded to two nitrogen atoms of ethylenediamine can be used. Examples of such star diblock copolymers include those represented by the general formula ((EO) _x (PO) _y ) ₂ NCH ₂ CH ₂ N ((PO) _y (EO) _x ) ₂ . Here, x and y represent the number of repetitions of EO and PO, respectively, x is preferably 5 to 110, y is preferably 15 to 70, x is 13 to 106, and y is 29 to 70. preferable.

Among such surfactants, since a mesoporous material having high pore ordering can be obtained, a salt (preferably a halide salt) of alkyltrimethylammonium [C _p H _{2p + 1} N (CH ₃ ) ₃ ]. ) Is preferably used. In that case, the alkyl group in the alkyltrimethylammonium preferably has 8 to 22 carbon atoms. Examples include octadecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, decyltrimethylammonium bromide, octyltrimethylammonium bromide, and docosyltrimethylammonium chloride. It is done.

  In the case of producing the Si-based polymer according to the present invention using the surfactant as described above, the organosilane precursor represented by the formula (2) is hydrolyzed in the solvent containing the surfactant. A porous precursor obtained by introducing the surfactant into the Si-based polymer is obtained by decomposing and condensing. The concentration of the surfactant in the solution is preferably 1 to 20% by mass. When the concentration of the surfactant is less than the lower limit, pore formation tends to be incomplete. On the other hand, when the concentration exceeds the upper limit, the amount of the unreacted surfactant remaining in the solution increases and becomes finer. There is a tendency that the uniformity of the holes tends to decrease.

  In the organic silica material of the present invention, the content of the Si polymer is preferably 10 to 80% by mass, and more preferably 30 to 70% by mass with respect to 100% by mass of the organic silica material. When the content of the Si-based polymer is less than the lower limit, the amount of light absorbed by the Si-based polymer tends to decrease. On the other hand, when the upper limit is exceeded, the order of the mesostructure tends to decrease. Moreover, 20-90 mass% is preferable with respect to 100 mass% of said organic silica type materials, and, as for the content rate of the said surfactant, 30-70 mass% is more preferable. When the content of the surfactant is less than the lower limit, the order of the mesostructure tends to be lowered, and the association of the organic groups in the Si-based polymer tends not to be sufficiently suppressed. There is a tendency that the amount of light absorbed by the polymer is likely to decrease.

  The organic silica material of the present invention may contain a polymerization inhibitor and / or an antioxidant as necessary. A conventionally well-known thing can be used as said polymerization inhibitor and antioxidant, For example, a phenol type compound is preferable and hydroquinone and its derivative (s) are preferable. By adding such a polymerization inhibitor and / or antioxidant, the stability of the organic silica-based material, for example, light resistance to light irradiation (particularly ultraviolet irradiation) tends to be improved.

  30 mass% or less is preferable with respect to 100 mass% of organic silica type materials, and, as for the content rate of the said polymerization inhibitor and antioxidant in the organic silica type material of this invention, 20 mass% or less is more preferable. When the content of the polymerization inhibitor and the antioxidant exceeds the upper limit, the quantum yield tends to decrease.

  The form of the organic silica material of the present invention is not particularly limited, and examples thereof include a particulate shape, a thin film shape, and a pattern shape obtained by patterning the thin film into a predetermined shape. The organic silica material of the present invention may be supported on mesoporous silica such as FSM.

  When producing the organic silica material of the present invention, the silane monomer may be polymerized after the silane monomer and the surfactant are mixed. As a result, the surfactant can be filled in the pores of the polymer of the silane monomer (Si polymer according to the present invention), and the quantum yield of the organic silica material can be kept high. .

  In the case of producing a thin-film organic silica material, first, the silane monomer is added to an acidic solution (such as an aqueous solution of hydrochloric acid or nitric acid or an alcohol solution) containing the surfactant, and the solution is stirred. Thus, the reaction (partial hydrolysis and partial condensation reaction) is carried out to produce a sol solution containing the partial polymer. Since such hydrolysis reaction of the silane monomer is likely to occur in a low pH region, partial polymerization can be promoted by lowering the pH of the system. At this time, the pH is preferably 6 or less, and more preferably 4 or less. Further, the reaction temperature at that time is preferably about 15 to 25 ° C., and the reaction time is preferably about 30 minutes to 1 day.

  Next, a thin-film organic silica-based material can be produced by applying the sol solution thus obtained to a substrate. The method for applying the sol solution to the substrate is not particularly limited, and various coating methods can be appropriately employed. Examples of the method include a solution casting method, a coating method using a bar coater, a roll coater, a gravure coater, and the like, a method such as dip coating, spin coating, and spray coating. Furthermore, it is also possible to form a patterned organic silica material on a substrate by applying a sol solution by an ink jet method.

  Next, the obtained thin film is preferably dried at about 25 to 120 ° C., and the polycondensation reaction of the partial polymer is advanced to form a three-dimensional crosslinked structure. The average film thickness of the obtained thin film is preferably 2 μm or less, and more preferably 0.1 to 0.5 μm.

  Such a thin-film organic silica-based material can also be obtained according to the method described in JP-A No. 2001-130911.

  Next, the organosilica mesoporous material of the present invention will be described. The organosilica mesoporous material of the present invention has the following formula (1):

It consists of the polymer (Si type polymer) of the organosilicon compound which has a repeating unit represented by these. In the organosilica mesoporous material of the present invention, Ar, L and R ^{1 to} R ⁶ in the formula (1) are Ar, L and R ¹ in the formula (1) of the organosilica material of the present invention. ~R ⁶ as synonymous.

  Such an organic silica-based mesoporous material can be produced by removing the surfactant from the organic silica-based material of the present invention. As a method for removing the surfactant, for example, (i) a mesostructured Si-based polymer and a surfactant are contained in an organic solvent (for example, ethanol) having high solubility in the surfactant. A method of removing the surfactant by immersing the organic silica material, (ii) firing the organic silica material of the present invention containing a mesostructured Si polymer and a surfactant at 250 to 550 ° C. And (iii) the organosilica material of the present invention containing a mesostructured Si polymer and a surfactant is immersed in an acidic solution (for example, dilute hydrochloric acid) and heated, An ion exchange method in which the surfactant is exchanged with hydrogen ions, and (iv) a heated acidic vapor (for example, hydrochloric acid vapor) of the organosilica material of the present invention containing a mesostructured Si polymer and a surfactant. After exposure to organic) Medium (e.g., ethanol) method was immersed in eluting the organic solvent the surfactant, and the like. The treatment conditions in these methods can be appropriately set depending on the type of surfactant, organic solvent, acidic vapor to be used.

  The form of the organic silica-based porous material of the present invention is not particularly limited, and examples thereof include a particulate shape, a thin film shape, and a pattern shape obtained by patterning the thin film into a predetermined shape. Depends on material form. Further, the organic silica based porous material of the present invention may be supported on mesoporous silica such as FSM.

  Moreover, when the organosilica mesoporous material of the present invention is produced as a powder, it may be used as it is, or may be molded and used as necessary. The means for molding is not particularly limited, but extrusion molding, tableting molding, rolling granulation, compression molding, CIP and the like are preferable. The shape can be determined according to the location and method of use, and examples thereof include a columnar shape, a crushed shape, a spherical shape, a honeycomb shape, an uneven shape, and a corrugated plate shape.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. The ultraviolet / visible absorption spectrum and emission spectrum of the obtained thin film were measured using “FP-6600 Spectrofluorometer” manufactured by JASCO.

(Synthesis Example 1)
<Synthesis of 1,3,6,8-tetrakis [4- (3-triethoxysilylpropylaminocarbonyloxy) phenyl] pyrene>
First, under an argon atmosphere, 1,3,6,8-tetrabromopyrene (4.14 g, 8.0 mmol), 4-methoxyphenylboronic acid (7.29 g, 48.0 mmol), K ₂ CO ₃ (8 .85 g, 64.0 mmol) and Pd (PPh ₃ ) ₄ (0.148 g, 0.128 mmol) were mixed and dehydrated 1,4-dioxane (80 ml) was added to the mixture. The mixture was stirred at 85 ° C. for 70 hours under an argon atmosphere and the following reaction formula (3):

The reaction represented by Then, after cooling to room temperature, the reaction product was poured into a mixture of concentrated hydrochloric acid and ice (volume ratio 1: 3) and stirred for 0.5 hour. Thereafter, the organic phase was extracted with chloroform, dried over anhydrous MgSO ₄ . MgSO ₄ was removed from the organic phase by filtration, and the solvent was distilled off with a rotary evaporator. The residue was recrystallized from toluene to obtain 1,3,6,8-tetrakis (4-methoxyphenyl) pyrene (4.65 g, yield 93%) as yellow crystals.

This 1,3,6,8-tetrakis (4-methoxyphenyl) pyrene was identified by ¹ H-NMR measurement. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.16 (s, 4H), 7.96 (s, 2H), 7.59 (d, J = 8.7 Hz, 8H), 7.07 (d, J = 8.7 Hz, 8H), 3.91 (s, 12H).

Next, 1,3,6,8-tetrakis (4-methoxyphenyl) pyrene (4.00 g, 6.38 mmol) was dissolved in distilled dichloromethane (300 ml), and then cooled to 0 ° C. A 1 mol / L BBr ₃ dichloromethane solution (32 ml) was gradually added dropwise to this solution, followed by stirring at 0 ° C. for 0.5 hour and then at room temperature for 15 hours.

The reaction represented by Subsequently, after heating and refluxing for 2 hours, the reaction product was cooled to room temperature, and water (200 ml) was added to stop the reaction. The resulting precipitate was collected by suction filtration, dissolved in ethanol, and reprecipitated by adding water. Thereafter, the precipitate was collected by suction filtration and vacuum-dried to obtain 1,3,6,8-tetrakis (4-hydroxyphenyl) pyrene (3.40 g, yield 93%) as a yellow-green solid.

This 1,3,6,8-tetrakis (4-hydroxyphenyl) pyrene was identified by ¹ H-NMR measurement. The results are shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 9.68 (s, 4H), 8.11 (s, 4H), 7.84 (s, 2H), 7.48 (d, J = 8. 5 Hz, 8H), 6.97 (d, J = 8.5 Hz, 8H).

  Next, 1,3,6,8-tetrakis (4-hydroxyphenyl) pyrene (0.80 g, 1.40 mmol), distilled dichloromethane (80 ml) and triethylamine (10 ml) were mixed, and this mixture was mixed with 3-triethoxy. Silylpropyl isocyanate (1.98 g, 8.00 mmol) was added, and the mixture was stirred at room temperature for 24 hours, then heated to reflux for 2 hours, and the following reaction formula (5):

The reaction represented by After the solvent was distilled off from the obtained solution with a rotary evaporator, toluene was added and stirred, and insolubles were removed by filtration. The operation of adding hexane to the obtained toluene solution and reprecipitation was repeated twice, and then the precipitate was collected by suction filtration, dried in vacuo and dried as a light yellow solid 1,3,6,8-tetrakis [4- ( 3-Triethoxysilylpropylaminocarbonyloxy) phenyl] pyrene (1.62 g, yield 74%) was obtained.

This 1,3,6,8-tetrakis [4- (3-triethoxysilylpropylaminocarbonyloxy) phenyl] pyrene was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement, IR measurement and MS measurement. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.16 (s, 4H), 7.97 (s, 2H), 7.63 (d, J = 8.3 Hz, 8H), 7.31 (d, J = 8.3 Hz, 8H), 5.59 (t, J = 5.9 Hz, 4H), 3.87 (q, J = 7.0 Hz, 24H), 3.33 (m, 8H), 1. 76 (m, 8H), 1.27 (t, J = 7.0 Hz, 36H), 0.73 (t, J = 8.0 Hz, 8H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 154.5, 150.5, 137.7, 136.4, 131.3, 129.6, 128.0, 125.8, 125.2, 121.4 58.4, 43.5, 23.0, 18.2, 7.6.
IR (ATR, cm ⁻¹ ): 3329 (NH st), 3039, 2974, 2928, 2885, 1716 (C═O st), 1533, 1489, 1203, 1165, 1070.
MS (MALDI, m / z): calcd for 15588.6790 [M] ⁺ , found 15588.6809.

(Synthesis Example 2)
After synthesizing 1,3,6,8-tetrakis (4-hydroxyphenyl) pyrene in the same manner as in Synthesis Example 1, this 1,3,6,8-tetrakis (4-hydroxyphenyl) pyrene (0.6 g, 1.05 mmol), distilled dimethylformamide (20 ml) and potassium carbonate (2.49 g, 18.0 mmol) were added, and allyl bromide (1.45 g, 12.0 mmol) was added to the mixture and stirred at room temperature for 20 hours. The following reaction formula (6):

The reaction represented by Water (100 ml) was added to the resulting reaction solution, and the deposited precipitate was collected by suction filtration and then washed with water and ethanol. The filter cake was heated and stirred in ethanol, then subjected to suction filtration, vacuum dried, and 1,3,6,8-tetrakis [4- (allyloxy) phenyl] pyrene (0.67 g, yield) as a pale yellow solid. 87%).

This 1,3,6,8-tetrakis [4- (allyloxy) phenyl] pyrene was identified by ¹ H-NMR measurement. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.15 (s, 4H), 7.95 (s, 2H), 7.58 (d, J = 8.7 Hz, 8H), 7.08 (d, J = 8.7 Hz, 8H), 6.13 (ddt, J = 17.4, 10.4, 5.4 Hz, 4H), 5.49 (dd, J = 17.4, 3.0 Hz, 4H) 5.34 (dd, J = 10.4, 3.0 Hz, 4H), 4.65 (d, J = 5.4 Hz, 8H).

  Next, 1,3,6,8-tetrakis [4- (allyloxy) phenyl] pyrene (0.6 g, 0.82 mmol), distilled tetrahydrofuran (20 ml) and triethoxysilane (0.82 g, 5.00 mmol) were added. Then, a platinum catalyst (platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in 3% by mass xylene, 50 mg) was added to the mixture, Stir for the following reaction formula (7):

The reaction represented by The resulting solution was cooled to room temperature and filtered through celite and activated carbon, and then the solvent was removed with a rotary evaporator, followed by vacuum drying to obtain 1,3,6,8-tetrakis [4- (3-tri Ethoxysilylpropyloxy) phenyl] pyrene (1.07 g, 94% yield) was obtained.

This 1,3,6,8-tetrakis [4- (3-triethoxysilylpropyloxy) phenyl] pyrene was identified by ¹ H-NMR measurement. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.16 (s, 4H), 7.96 (s, 2H), 7.57 (d, J = 8.4 Hz, 8H), 7.07 (d, J = 8.4 Hz, 8H), 4.06 (t, J = 6.5 Hz, 8H), 3.88 (q, J = 7.0 Hz, 24H), 2.0 (m, 8H), 1. 76 (m, 8H), 1.27 (t, J = 7.0 Hz, 36H), 0.85 (m, 8H).

Example 1
<Preparation of a thin film comprising tetraphenylpyrene skeleton-containing Si-based polymer / surfactant Brij76>
1,3,6,8-tetrakis [4- (3-triethoxysilylpropylaminocarbonyloxy) phenyl obtained in Synthesis Example 1 was added to a mixed solvent of tetrahydrofuran and ethanol (mass ratio 1: 1, 1.0 g). Pyrene (30 mg), nonionic surfactant Brij76 (trade name, manufactured by Aldrich, chemical formula: C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₁₀ H, 20 mg), 2 mol / L hydrochloric acid (4 μl) and pure water (20 μl) was added and mixed, and the mixture was stirred at room temperature for 24 hours to prepare a sol solution.

  The obtained sol solution was applied onto a quartz substrate and a glass substrate by spin casting (rotation speed: 4000 rpm, 30 seconds) or solution casting, respectively, and tetraphenylpyrene skeleton-containing Si-based polymer / surfactant Brij76. A thin film was obtained.

  The ultraviolet / visible absorption spectrum (dotted line) and the emission spectrum (solid line) of this thin film with respect to 400 nm excitation light are shown in FIG. 1, and the X-ray diffraction pattern is shown in FIG. The obtained thin film had absorption in the region from near ultraviolet to visible light centered around 390 nm, and exhibited blue light emission around 450 nm. The fluorescence quantum yield when excited with light of 400 nm was 0.75. Further, as apparent from the results shown in FIG. 2, it was confirmed that this thin film had a mesostructure with a period of about 8.3 nm.

When this thin film was continuously irradiated with light of 400 nm in the atmosphere (3 J / cm ² , 0.05 mW / cm ² × 16.7 hours), the absorption intensity at 400 nm after the light irradiation was 95% or more before the light irradiation. In other words, this thin film was confirmed to exhibit excellent light resistance.

(Example 2)
<Preparation of Thin Film Containing Tetraphenylpyrene Skeleton-Containing Si Polymer / Surfactant P123>
Nonionic surfactant P123 (trade name instead of the nonionic surfactant Brij76, manufactured by Aldrich, chemical _{formula: HO (CH 2 CH 2 O} ) 20 (CH 2 CH (CH 3) O) 70 (CH 2 CH 2 A thin film made of tetraphenylpyrene skeleton-containing Si polymer / surfactant P123 was obtained in the same manner as in Example 1 except that O) ₂₀ H, 20 mg) was used.

  The ultraviolet / visible absorption spectrum (dotted line) of this thin film and the emission spectrum (solid line) with respect to 400 nm excitation light are shown in FIG. 3, and the X-ray diffraction pattern is shown in FIG. The obtained thin film had absorption in the region from near ultraviolet to visible light centered around 390 nm, and exhibited blue light emission around 450 nm. The fluorescence quantum yield when excited with light of 400 nm was 0.70. Further, as apparent from the results shown in FIG. 4, it was confirmed that this thin film had a mesostructure with a period of about 8.8 nm.

When this thin film was continuously irradiated with light of 400 nm in the atmosphere (3 J / cm ² , 0.05 mW / cm ² × 16.7 hours), the absorption intensity at 400 nm after the light irradiation was 95% or more before the light irradiation. In other words, this thin film was confirmed to exhibit excellent light resistance.

(Example 3)
<Fabrication of Thin Film Containing Tetraphenylpyrene Skeleton-Containing Si Polymer / Surfactant P123>
1,3,6,8-tetrakis [4- (3-triethoxysilyl) instead of 1,3,6,8-tetrakis [4- (3-triethoxysilylpropylaminocarbonyloxy) phenyl] pyrene (30 mg) A thin film made of a tetraphenylpyrene skeleton-containing Si polymer / surfactant P123 was prepared in the same manner as in Example 2 except that propylaminocarbonyloxy) phenyl] pyrene (15 mg) and tetraethoxysilane (15 mg) were used. Obtained.

  FIG. 5 shows an ultraviolet / visible absorption spectrum (dotted line) and an emission spectrum (solid line) for excitation light of 400 nm, and FIG. 6 shows an X-ray diffraction pattern. The obtained thin film had absorption in the region from near ultraviolet to visible light centered around 390 nm, and exhibited blue light emission around 450 nm. The fluorescence quantum yield when excited with light of 400 nm was 0.75. Further, as apparent from the results shown in FIG. 6, it was confirmed that this thin film had a mesostructure with a period of about 8.5 nm.

When this thin film was continuously irradiated with light of 400 nm in the atmosphere (3 J / cm ² , 0.05 mW / cm ² × 16.7 hours), the absorption intensity at 400 nm after the light irradiation was 95% or more before the light irradiation. In other words, this thin film was confirmed to exhibit excellent light resistance.

Example 4
<Preparation of tetraphenylpyrene skeleton-containing Si-based porous body>
The thin film produced in Example 3 was exposed to hydrochloric acid vapor at 80 ° C. for 12 hours, and then immersed in ethanol at 60 ° C. for 12 hours together with the substrate to elute the surfactant P123 in the thin film. The thin film was taken out from ethanol together with the substrate and dried at room temperature to obtain a tetraphenylpyrene skeleton-containing Si-based porous body.

When the infrared absorption spectrum of this Si-based porous material was measured, the absorption band of CH stretching vibration (near 2870-2950 cm ⁻¹ ) of the surfactant P123 almost disappeared, so that the surfactant P123 was sufficiently removed. It was confirmed that

  FIG. 7 shows an ultraviolet / visible absorption spectrum (dotted line) and an emission spectrum (solid line) of the porous body with respect to 400 nm excitation light, and FIG. 8 shows an X-ray diffraction pattern. The obtained porous body had absorption in the region from near ultraviolet to visible light centered around 400 nm and exhibited blue light emission around 475 nm. The fluorescence quantum yield when excited with light of 400 nm was 0.21. Further, as apparent from the results shown in FIG. 8, it was confirmed that this thin film had a mesoporous structure with a period of about 7.7 nm.

When the porous body was continuously irradiated with 400 nm light in the atmosphere (3 J / cm ² , 0.05 mW / cm ² × 16.7 hours), the absorption intensity at 400 nm after the light irradiation was 95% or more before the light irradiation. It was confirmed that this porous body exhibited excellent light resistance.

(Comparative Example 1)
<Preparation of thin film comprising pyrene skeleton-containing Si-based polymer / surfactant Brij76>
In place of 1,3,6,8-tetrakis [4- (3-triethoxysilylpropylaminocarbonyloxy) phenyl] pyrene, the following formula (8):

1,6-bis (triethoxysilyl) pyrene (100 mg) represented by the following formula: 2.0 g of a mixed solvent of tetrahydrofuran and ethanol (mass ratio 1: 1) was added to 2.0 g of the nonionic surfactant Brij76. The pyrene skeleton-containing Si polymer / polymer was changed in the same manner as in Example 1 except that the amount was changed to 70 mg, the amount of 2 mol / L hydrochloric acid to 5 μl, the amount of pure water to 21 μl, and the stirring time to 15 hours. A thin film made of the surfactant Brij76 was obtained.

  FIG. 9 shows an ultraviolet / visible absorption spectrum (dotted line) and an emission spectrum (solid line) of the thin film with respect to 400 nm excitation light, and FIG. 10 shows an X-ray diffraction pattern. The obtained thin film showed almost no absorption in the visible light region of 400 nm or more. When excited with light of 340 nm, the fluorescence quantum yield was 0.06. Further, as apparent from the results shown in FIG. 10, it was confirmed that this thin film had a mesostructure with a period of about 6.5 nm.

(Comparative Example 2)
<Preparation of thin film made of anthracene skeleton-containing Si polymer / surfactant Brij76>
In place of 1,3,6,8-tetrakis [4- (3-triethoxysilylpropylaminocarbonyloxy) phenyl] pyrene, the following formula (9):

9,10-bis (triethoxysilyl) anthracene (50 mg) represented by the following formula, the amount of the mixed solvent of tetrahydrofuran and ethanol (mass ratio 1: 1) was adjusted to 2.0 g, and the nonionic surfactant Brij76 From the anthracene skeleton-containing Si-based polymer / surfactant Brij76, except that the amount was changed to 43 mg, the amount of 2 mol / L hydrochloric acid to 2.5 μl, and the amount of pure water to 22 μl, respectively. A thin film was obtained.

  An ultraviolet / visible absorption spectrum (dotted line) and an emission spectrum (solid line) with respect to 400 nm excitation light of this thin film are shown in FIG. 11, and an X-ray diffraction pattern is shown in FIG. The obtained thin film had absorption in the region from near ultraviolet to visible light centered around 380 nm and emitted light around 540 nm. However, the fluorescence quantum yield when excited with 400 nm light is 0.07, and it is assumed that most of the excitation energy is thermally deactivated. Further, as apparent from the results shown in FIG. 12, it was confirmed that this thin film had a mesostructure with a period of about 6.6 nm.

When this thin film was continuously irradiated with light of 400 nm in the atmosphere (3 J / cm ² , 0.05 mW / cm ² × 16.7 hours), the absorption intensity at 400 nm after the light irradiation decreased to 35% before the light irradiation. In addition, decomposition of organic groups in the thin film due to light irradiation was observed.

(Comparative Example 3)
<Preparation of Thin Film Containing Oligophenylene Vinylene Skeleton-Containing Si Polymer / Surfactant P123>
In place of 1,3,6,8-tetrakis [4- (3-triethoxysilylpropylaminocarbonyloxy) phenyl] pyrene, the following formula (10):

1,4-bis (4-triethoxysilylstyryl) -2,5-bis (hexyloxy) benzene (25 mg) represented by the following formula: the amount of tetraethoxysilane is 100 mg, and a mixed solvent of tetrahydrofuran and ethanol The amount of (mass ratio 1: 1) was changed to 2.0 g, the amount of nonionic surfactant P123 was changed to 60 mg, the amount of 2 mol / L hydrochloric acid was changed to 1 μl, and the amount of pure water was changed to 11 μl. In the same manner as in Example 3, a thin film comprising an oligophenylene vinylene skeleton-containing Si polymer / surfactant P123 was obtained.

  FIG. 13 shows an ultraviolet / visible absorption spectrum (dotted line) and an emission spectrum (solid line) of the thin film for 400 nm excitation light, and FIG. 14 shows an X-ray diffraction pattern. The obtained thin film had absorption in the region from near ultraviolet to visible light centered around 400 nm, and exhibited blue light emission around 490 nm. The fluorescence quantum yield when excited with light of 400 nm was 0.61. Further, as apparent from the results shown in FIG. 14, it was confirmed that this thin film had a mesostructure with a period of about 11.2 nm.

When the thin film was continuously irradiated with 400 nm light in the atmosphere (3 J / cm ² , 0.05 mW / cm ² × 16.7 hours), the absorption intensity at 400 nm after the light irradiation decreased to 31% before the light irradiation. In addition, decomposition of organic groups in the thin film due to light irradiation was observed.

(Comparative Example 4)
<Preparation of a thin film composed of an acridone skeleton-containing Si-based polymer / surfactant P123>
In place of 1,3,6,8-tetrakis [4- (3-triethoxysilylpropylaminocarbonyloxy) phenyl] pyrene, the following formula (11):

The amount of the mixed solvent of tetrahydrofuran and ethanol (mass ratio 1: 1) is 1.5 g, and the nonionic surfactant P123 is used. The acridone skeleton-containing Si-based weight was changed in the same manner as in Example 2 except that the amount was 83 mg, the amount of 2 mol / L hydrochloric acid was 10 μl, the amount of pure water was 43 μl, and the stirring time was 0.5 hours. A thin film made of the coalescence / surfactant P123 was obtained.

  FIG. 15 shows the ultraviolet / visible absorption spectrum (dotted line) and emission spectrum (solid line) of the thin film for 400 nm excitation light, and FIG. 16 shows the X-ray diffraction pattern. The obtained thin film had absorption in the region from near ultraviolet to visible light centered around 400 nm, and also emitted light near 500 nm. However, the fluorescence quantum yield when excited with light of 400 nm is 0.03, and it is assumed that most of the excitation energy is thermally deactivated. Further, as apparent from the results shown in FIG. 16, it was confirmed that this thin film had a mesostructure with a period of about 9.6 nm.

When this thin film was continuously irradiated with light at 400 nm in the atmosphere (3 J / cm ² , 0.05 mW / cm ² × 16.7 hours), the absorption intensity at 400 nm after light irradiation was higher than that before light irradiation. Almost no decline.

  In Table 1, the said result about the thin film obtained in Examples 1-3 and Comparative Examples 1-4 and the porous body obtained in Example 4 was put together.

  As apparent from the results shown in FIGS. 1 to 16 and Table 1, when the Si-based polymer having a tetraarylene skeleton according to the present invention was used (Examples 1 to 3), the obtained organic silica-based The material contained a mesostructured Si-based polymer, absorbed light in the region from near ultraviolet to visible light, had a high fluorescence quantum yield, and was excellent in light resistance. Also, in the case of the organic silica-based porous material using the Si-based polymer having a tetraarylene skeleton according to the present invention (Example 4), light in the region from near ultraviolet light to visible light is absorbed and light resistance is improved. It was excellent.

  On the other hand, when the Si-based polymer having a pyrene skeleton is used instead of the tetraarylene skeleton according to the present invention (Comparative Example 1), the obtained organic silica-based material cannot absorb visible light. there were. In the case of using an Si-based polymer having an anthracene skeleton or an oligophenylene vinylene skeleton (Comparative Examples 2 to 3), the obtained organic silica-based material absorbs visible light. It was inferior to. Furthermore, in the case of using an Si-based polymer having an acridone skeleton (Comparative Example 4), the obtained organic silica-based material absorbed visible light and was excellent in light resistance. Was very low.

  As described above, according to the present invention, the organic silica-based material and the organic silica-based porous body are excellent in light resistance, and efficiently absorb light in the region (wavelength 360 to 500 nm) from near ultraviolet to visible light. It becomes possible to do.

  Therefore, since the organic silica-based material and the organic silica-based porous body of the present invention are excellent in light resistance and visible light absorption, particularly visible light-responsive photoelectric conversion such as light-emitting materials and photoelectric conversion materials (photocatalysts and solar cells). It is useful as a material.

2 is a graph showing an ultraviolet / visible absorption spectrum and an emission spectrum for 400 nm excitation light of the Si-based polymer thin film obtained in Example 1. FIG. 2 is a graph showing an X-ray diffraction pattern of the Si-based polymer thin film obtained in Example 1. It is a graph which shows the emission spectrum with respect to the ultraviolet / visible absorption spectrum and 400 nm excitation light of the Si type polymer thin film obtained in Example 2. 4 is a graph showing an X-ray diffraction pattern of the Si-based polymer thin film obtained in Example 2. It is a graph which shows the emission spectrum with respect to the ultraviolet / visible absorption spectrum and 400 nm excitation light of the Si type polymer thin film obtained in Example 3. 4 is a graph showing an X-ray diffraction pattern of a Si-based polymer thin film obtained in Example 3. It is a graph which shows the emission spectrum with respect to the ultraviolet / visible absorption spectrum and 400 nm excitation light of the Si type polymer thin film obtained in Example 4. 4 is a graph showing an X-ray diffraction pattern of a Si-based polymer thin film obtained in Example 4. 4 is a graph showing an ultraviolet / visible absorption spectrum and an emission spectrum for excitation light of 340 nm of the Si-based polymer thin film obtained in Comparative Example 1. 4 is a graph showing an X-ray diffraction pattern of a Si-based polymer thin film obtained in Comparative Example 1. It is a graph which shows the emission spectrum with respect to the ultraviolet / visible absorption spectrum and 400 nm excitation light of the Si type polymer thin film obtained in Comparative Example 2. 6 is a graph showing an X-ray diffraction pattern of a Si-based polymer thin film obtained in Comparative Example 2. It is a graph which shows the emission spectrum with respect to the ultraviolet / visible absorption spectrum and 400 nm excitation light of the Si type polymer thin film obtained in Comparative Example 3. 6 is a graph showing an X-ray diffraction pattern of a Si-based polymer thin film obtained in Comparative Example 3. It is a graph which shows the emission spectrum with respect to the ultraviolet / visible absorption spectrum and 400 nm excitation light of the Si type polymer thin film obtained in Comparative Example 4. 6 is a graph showing an X-ray diffraction pattern of a Si-based polymer thin film obtained in Comparative Example 4.

Claims (4)

Following formula (1):

(In the formula (1), Ar represents each independently an arylene group selected from the group consisting of a phenylene group, a biphenylylene group, and a naphthylene group, and the arylene group may have a substituent; Each independently represents a divalent aliphatic organic group, an alkylene group or a single group comprising at least one group selected from the group consisting of an ether group, a thioether group, a carbonyl group, a carbonate group, an amino group, an amide group and a urethane group. Represents a bond, and R ^{1 to} R ⁶ each independently represents one type of substituent selected from the group consisting of an alkyl group, an alkoxy group, an amino group, a nitro group, and a cyano group, a halogen atom, or a hydrogen atom.
An organosilica-based material comprising a polymer of a mesostructured organosilicon compound having a repeating unit represented by formula (II) and a surfactant. 2. The organosilica-based material according to claim 1, wherein Ar in the formula (1) is a phenylene group, and R ^{1 to} R ⁶ are hydrogen atoms. Following formula (1):

(In the formula (1), each Ar independently represents one arylene group selected from the group consisting of a phenylene group, a biphenylylene group, and a naphthylene group, and the arylene group may have a substituent, Each independently represents a divalent aliphatic organic group, an alkylene group or a single group comprising at least one group selected from the group consisting of an ether group, a thioether group, a carbonyl group, a carbonate group, an amino group, an amide group and a urethane group. R ^{1 to} R ⁶ each independently represent a substituent selected from the group consisting of an alkyl group, an alkoxy group, an amino group, a nitro group, and a cyano group, a halogen atom, or a hydrogen atom.
An organic silica-based mesoporous material comprising a polymer of an organosilicon compound having a repeating unit represented by the formula: The organosilica mesoporous material according to claim 3, wherein Ar in the formula (1) is a phenylene group, and R ^{1 to} R ⁶ are hydrogen atoms.

Images