JPH07196348A - Reactive inorganic filler and method for producing the same - Google Patents

Abstract

(57) [Summary] [Purpose] A novel reactive inorganic filler that is promising as a new material for cement replacement, and a method for producing the same. In particular, an inorganic filler having improved reactivity capable of giving an inorganic molded product by solidifying by reacting better with a silicic acid oligomer blocked with a trimethylsilyl group or phosphoric acid or a phosphoric acid ester group, and a method for producing the same. provide. [Composition] In order to improve the reactivity of the inorganic filler such as diatomaceous earth and silica sand, the material for the inorganic filler is (1) treated with an activation-imparting agent such as silicon halide to be activated, and then ammonia if necessary. Alternatively, it is reacted with an amine compound or treated with (2) an acid or a base.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel reactive inorganic filler, which is promising as a new cement substitute material, and a method for producing the same. The present invention, in particular, an inorganic filler having an improved reactivity capable of giving an inorganic molded article by reacting well with a silicic acid oligomer which is blocked by a trimethylsilyl group or a phosphoric acid or a phosphoric acid ester group, and solidified, and There is in providing the manufacturing method. The present invention is also to provide an inorganic material product having a high strength and yet having a toughness.

[0002]

2. Description of the Related Art Sols made of inorganic materials obtained by hydrolyzing metal alkoxides such as silicon alkoxides or inorganic material derived therefrom are excellent in heat resistance and combustion resistance. It is also known to have radiation resistance, high hardness, and abrasion resistance. Such inorganic material substances also have oil resistance and solvent resistance, and by taking advantage of these characteristics, heat resistant materials, non-combustible materials, heat ray reflective materials, electrical insulating materials, transparent conductive materials, anticorrosive materials, chemical resistance imparting materials. It is expected to be used as a surface protection material having abrasion resistance, and a special function material having anti-reflection and lubricating action. Utilization development of these inorganic material substances is currently under way by making use of their characteristics. By hydrolyzing or polycondensing such a metal alkoxide that is a liquid raw material, it is possible to convert from a sol state in which fine particles are dispersed in a liquid medium to a gel state where the sol is solidified, The gel thus obtained is used as it is, or is further heated or the like to form a solid glass or ceramic which is an inorganic material. This is generally called the sol-gel method.

However, for example, an inorganic material obtained by hydrolyzing a metal alkoxide such as tetraethoxysilane by a usual method has a drawback that the obtained material is brittle as a result of three-dimensional polymerization. Have
Glass, ceramics, etc. obtained by using such a conventional method have a three-dimensional three-dimensional structure, and have become hard and brittle as described above. Furthermore, in order to make it cheaper, it is necessary to adopt a simple method using an inorganic material from the stage of the raw material as much as possible.

The present inventors, when polymerizing a metal alkoxide having many functional groups such as silicon alkoxide to produce an inorganic material, have a linear product structure, that is, a unit. As a result of earnest research to produce an inorganic material having a structure in which the components are linearly connected as long as possible in one dimension, as a result, many functional groups such as silicon alkoxide using alkylsilyl halides such as trimethylsilyl chloride were used. We succeeded in producing an inorganic material substance (polysiloxane oligomer) having a uniform and reproducible linear structure by a simple method of controlling the hydrolysis and polycondensation reaction of a metal alkoxide having a. Based on this result, the inventors of the present invention include only an inorganic material by using an inorganic blocking agent such as phosphoric acid or a phosphoric acid ester in order to synthesize a complete inorganic silicic acid polymer that can be used in a large amount at an even lower cost. , Attempted to manufacture an inorganic material using an inexpensive material. The inorganic silicic acid polymer (polysiloxane oligomer) having various advantageous properties finally synthesized in this manner has a large surface area and high surface activity, and can be obtained inexpensively in large quantities in the future. It is advantageous to subject the inorganic filler to the curing reaction with the above-mentioned inorganic filler which is environmentally friendly.

[0005]

Means for Solving the Problems The present inventors have proposed a unit component obtained by utilizing a blocking reaction using a blocking agent such as an alkylsilyl halide such as trimethylsilyl chloride or an inorganic blocking agent such as phosphoric acid or a phosphoric acid ester. A search was conducted for inorganic silicic acid polymers (polysiloxane oligomers) having a linear structure that is one-dimensionally long and as long as possible, and various inorganic fillers that have a hardening reactivity. As a result, the surface of diatomaceous earth, silica sand, etc. is medium. We found that there was a problem that the reactivity was very low, and we concluded that there was a problem with that reactivity. The present inventors have conducted earnest research to develop a method for improving the reactivity of inorganic fillers such as diatomaceous earth and silica sand, which have low reactivity in the reaction with the polysiloxane oligomer, and as a result, the results are extremely simple. It was found that the reactivity can be improved by various methods, and the present invention was completed.

In the present invention, in order to improve the reactivity of the inorganic filler such as diatomaceous earth and silica sand, the inorganic filler material is treated with (1) an activation-imparting agent such as silicon halide and then activated. If necessary, it is reacted with ammonia or an amine compound, or treated with (2) acid or base. The above method (1) is carried out by using a silicic acid-containing inorganic filler such as diatomaceous earth, silica sand, silicic acid-containing volcanic ash, fly ash, silica rock, and quartz, a silicon halide such as silicon tetrachloride, silicon tetrabromide, or trichlorosilane. Such as halogenated silanes, and trimethylchlorosilane and other alkylhalogenosilanes, etc., to activate the surface of the inorganic filler, and then, if necessary, aqueous ammonia solution, ammonia gas, etc. Ammonia or a compound selected from the group consisting of amine compounds such as methylamine and hydroxymethylamine.

In the reaction between the activation imparting agent and the inorganic filler, it is preferable to use the activation imparting agent in an amount sufficient to activate the surface of the inorganic filler. For example, when silicon tetrachloride is used as the activation imparting agent, about 1 to 8 g, preferably about 2 to 6 g, and more preferably about 3 to 5 g can be used for 1 g of diatomaceous earth. Depending on the type of diatomaceous earth, the amount used may be selected as appropriate. When silicon tetrachloride is used as the activation imparting agent, for example, when silica sand is used as the inorganic filler, about 0.2 to 5 g, preferably about 0.5 g per 1 g of silica sand. ~ 3g, more preferably about 0.8-2g
It can be used, but the amount used can be appropriately selected depending on the type of silica sand used. The container containing these mixtures is then allowed to stand for about 5 minutes to about 2 hours, preferably about 15 minutes to about 1 hour, more preferably about 2 minutes.
Ultrasonic irradiation can be performed for 5 minutes to about 50 minutes. In the ultrasonic irradiation treatment, the optimum conditions can be appropriately determined by experiments depending on the irradiation energy or the type of apparatus used. Instead of ultrasonic irradiation, other known reaction promoting means may be applied.

Unreacted silicon tetrachloride in these mixtures can then be removed by applying known means, for example vacuum decompression. The inorganic filler treated with silicon tetrachloride thus obtained may be further treated with, for example, ammonia gas for about 5 minutes to about 2 hours, preferably for about 15 minutes to about 1 hour, more preferably for about 25 minutes to about 50 hours. Can be contacted for minutes. The contact reaction time can be appropriately determined by an experiment under optimal conditions. The treated filler thus obtained is a one-dimensional unit component obtained by utilizing a blocking reaction using a blocking agent such as an alkylsilyl halide such as trimethylsilyl chloride or an inorganic blocking agent such as phosphoric acid or a phosphoric acid ester as much as possible. It is used in a curing reaction with an inorganic silicic acid polymer (polysiloxane oligomer) having a long linear structure and gives an inorganic molded body.

For example, when diatomaceous earth and silica sand are used as the inorganic fillers, silicon tetrachloride is added in an amount of 4 g to diatomaceous earth and 1 g to silica sand to 1 g of each. Next, after sonicating the container containing these mixtures for 30 minutes, unreacted silicon tetrachloride can be removed under reduced pressure in a vacuum. The inorganic filler treated with silicon tetrachloride thus obtained is contacted with ammonium gas for 30 minutes. This treated filler is obtained by utilizing a blocking reaction with a blocking agent such as trimethylsilyl chloride or phosphoric acid or phosphoric acid ester described below, and a polysiloxane oligomer having a structure in which unit components are linearly connected in a linear manner as long as possible. It is used for curing reaction with and gives an inorganic molding.

In the method (2), a silicic acid-containing inorganic filler such as diatomaceous earth, silica sand, silicic acid-containing volcanic ash, fly ash, silica rock or quartz is treated with an acid or a base,
The surface of the inorganic filler is activated and the surface of the filler rich in silicic acid is enriched with silanol groups (Si-OH groups). As described above, the surface of the inorganic filler is activated, and the silanol groups on the surface of the inorganic filler can react with the polysiloxane oligomer to efficiently form a chemical bond. As the acid, hydrochloric acid, bromic acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, bisulfate, acidic sulfite, peroxosulfuric acid, chromic acid, inorganic acids such as permanganic acid or salts thereof, acetic acid, butyric acid, Examples thereof include organic acids such as formic acid, oxalic acid, succinic acid, fumaric acid, benzoic acid, trifluoroacetic acid and the like. As the acid, strong acids such as hydrochloric acid, sulfuric acid and nitric acid are preferable, and concentrated hydrochloric acid, concentrated sulfuric acid and concentrated nitric acid can be preferably used. Of these, hydrochloric acid can be preferably used.

When natural silica sand is used as the inorganic filler and concentrated hydrochloric acid is used as the acid, the surface of the natural silica sand will have --SiOH groups and --SiOM.
Both (M is a metal ion) group and -Si-O-Si group are present. However, when treated with hydrochloric acid, the following reactions occur and surface OH groups increase on the surface of the silica sand.

[0012]

[Chemical 2]

The silanol groups on the surface can react with the polysiloxane oligomer to form chemical bonds efficiently. As the base, sodium hydroxide,
Potassium hydroxide, lithium hydroxide, calcium hydroxide,
Examples thereof include inorganic bases such as barium hydroxide, magnesium hydroxide and ammonium hydroxide, and organic bases such as methylamine, ethylamine, hydroxyamine and triethylamine. Especially as a base, sodium hydroxide,
Potassium hydroxide, lithium hydroxide, calcium hydroxide,
A strong base such as barium hydroxide is preferred, and concentrated sodium hydroxide aqueous solution, concentrated potassium hydroxide aqueous solution and the like can be used. Among them, concentrated sodium hydroxide aqueous solution can be preferably used. When treated with a base, it is preferably neutralized with an acid. The acid can be selected from the above and used. When natural silica sand is used as the inorganic filler and a sodium hydroxide aqueous solution is used as the base, the -Si-O-Si group on the surface of the natural silica sand is hydrolyzed by NaOH treatment and then neutralized. The following reactions occur through the steps, and surface OH groups increase on the surface of the silica sand.

[0014]

[Chemical 3]

The silanol groups on the surface can react with the polysiloxane oligomer to efficiently form a chemical bond. As the inorganic filler, those having a high silicic acid content can be preferably used, and the diatomaceous earth, silica sand, silicic acid-containing volcanic ash, fly ash, silica rock, quartz, etc. can be used, and selected from artificial or natural ones. Can be used. As the inorganic filler, one having strength in its material itself is preferable, and one which is stable once formed into a molded product can be suitably used. The inorganic filler is preferably clean, strong, and durable, more preferably strong, hard, and solid, and can be selected from those commonly known and easily available. As the inorganic filler, those that normally fall within the category of fine aggregate can be preferably used, but the particle size is the particle shape of the inorganic filler used, its surface state, polysiloxane oligomer used together, other admixtures or admixtures, etc. It can be appropriately selected and used according to. As the above-mentioned inorganic filler, powdery one can also be preferably used.

The reactive inorganic filler obtained as described above can be reacted with the following polysiloxane oligomer. The reaction may be a mixture of both under hydrolysis conditions. The mixing ratio of the two may be appropriately selected according to the purpose, or other additives may be added. The additives may include those known in the field of cement. The polysiloxane oligomer is
Typically, it is obtained by hydrolyzing a silicon alkoxide under polycondensation conditions, and then treating the obtained silicic acid polycondensate with a blocking reagent consisting of a trialkylsilyl halide at least once. The step of treating with a blocking reagent containing this trialkylsilyl halide can be repeated after the partial hydrolysis reaction of the polysiloxane oligomer obtained by treating with the blocking reagent again under polycondensation conditions.

Further, the polysiloxane oligomer is
Typically, a silicon alkoxide was hydrolyzed under polycondensation reaction conditions to form a silicic acid polycondensation oligomer, and the resulting silicic acid polycondensation oligomer product was partially hydrolyzed. It is obtained by subjecting a partially hydrolyzed silicic acid polycondensation oligomer product to a blocking treatment with phosphoric acid or a phosphoric acid ester at least once. In this case, the polysiloxane oligomer obtained by the blocking treatment can be partially hydrolyzed before use. Preferably, the silicic acid polycondensation oligomer has a linear structure, and further has a structure in which the unit components are linearly connected at least as long as possible in one dimension. The polysiloxane oligomer has the general formula

[Chemical 4] (In the formula, i is 1 to 20, m is 0 to 20, R may be the same or different, and is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 1 to 10 carbon atoms, or -Si. (OR) ₃
Or —PO (OR ¹ ) ₂ and at least one of R is —PO (OR ¹ ) ₂ and R ¹ may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon atom. Number 1
10 to 10 aralkyl groups, —PO (OR ¹ ) ₂ or —Si
A silicic acid ester represented by (OR) ₃ ). This one has the corresponding silicate ester
It is obtained by blocking treatment with phosphoric acid or phosphoric acid ester at least once. In this case, the silicic acid ester obtained by the blocking treatment can be partially hydrolyzed before use. First, in the hydrolysis reaction of the silicon alkoxide under polycondensation conditions, the silicon alkoxide is partially reacted with water to synthesize a polysiloxane oligomer.

The silicon alkoxide is one in which at least one alkoxy group is bonded to a silicon atom,
Preferred are those in which at least two alkoxy groups are bonded to a silicon atom, and a typical example is tetraalkoxysilane. Examples of the tetraalkoxysilane include tetraethoxysilane, tetramethoxysilane, tetra-n-propoxysilane, tetra-
i-propoxysilane, tetra-n-butoxysilane,
Tetra-sec-butoxysilane, tetra-t-butoxysilane, tetra-i-amyloxysilane, tetra-n
-Octyloxysilane, tetra-n-nonyloxysilane, n-butoxytri-t-butoxysilane, diethoxydi-t-butoxysilane, dimethoxydi-t-butoxysilane, diethoxyditrityloxysilane and the like. For example, as the alkoxysilane, tetraethoxysilane, tetramethoxysilane and the like can be preferably used. As the silicon alkoxide, in addition to the above tetraalkoxysilane monomer, a low amount condensate such as 2 monomers, 3 monomers, 4 monomers and 5 monomers, or a monomer may be included. It may be a mixture in any proportion thereof. A linear condensate is preferably used as the low molecular weight condensate.

In synthesizing this polysiloxane oligomer, the starting silicon alkoxide is preferably reacted with water in the presence of an organic solvent. In that case, it is preferable to use as little water and organic solvent as possible with respect to the starting silicon alkoxide. The reaction is preferably carried out under acidic conditions. The reaction system can be made acidic by adding an acid. As the acid, hydrochloric acid, bromic acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, bisulfate, inorganic acids such as acid sulfites or salts thereof, acetic acid, butyric acid, formic acid, oxalic acid, succinic acid, fumaric acid, Examples thereof include organic acids such as benzoic acid. Of these, hydrochloric acid can be preferably used.

The organic solvent which can be used in this reaction includes methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and t.
-Butanol, pentanol, hexanol, heptanol, octanol, decanol and other aliphatic alcohols, cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol and other alicyclic alcohols, or mixtures thereof. To be As the organic solvent, methanol, ethanol or the like can be preferably used.

In the polysiloxane oligomer synthesis reaction, an appropriate amount of organic solvent and water are added to the starting silicon alkoxide, and then an appropriate amount of acid is added to the mixture,
Stir vigorously for about 10 minutes to about 1 hour, preferably about 20 minutes to about 40 minutes, more preferably about 2
React for 5 to 35 minutes to form a uniform reaction mixture,
Then mix the homogenized reaction mixture from about 5 ° C to about 80 ° C.
C., preferably about 15 ° C. to about 50 ° C., more preferably about 20 ° C. to about 40 ° C., with gentle stirring or shaking for about 5 hours to about 100 hours, preferably about 10 hours to about 50 hours. , And more preferably about 10
The reaction is continued for about 50 hours. Depending on the type of alkoxide group in the silicon alkoxide used, the reaction time also needs to be longer. In general, those having an alcohol residue having a large number of carbon atoms require a long reaction time, but the reaction time can be changed by adjusting the amount and type of coexisting water, organic solvent, and acid.

In this polysiloxane oligomer synthesis reaction, the organic solvent is about 0.5 times to about 10 times, preferably about 0.7 times, the mole of the starting silicon alkoxide.
The molar amount is about 5 to about 5 times, more preferably about 0.9 to about 2 times. During the polysiloxane oligomer synthesis reaction, water is about 0.8 times to about 10 times, preferably about 1.0 times, the starting silicon alkoxide.
The molar amount is about 5 times to about 5 times, more preferably about 1.5 times to about 3 times. The amount of acid added in this reaction is from about 0.001 times to about 5 times, preferably from about 0.005 times to about 2 times, more preferably from about 0.01 times, the starting silicon alkoxide. It is used at about 0.5 times the molar amount.

Next, the polysiloxane oligomer product thus obtained is treated with a blocking reagent to synthesize a block-treated polysiloxane oligomer product. The blocking reagent that can be used in this reaction can be selected from those known as blocking reagents for inorganic metals such as silicon, and can be used as long as it is compatible with such purpose. It can be used by selecting from reagents that are easily available. As such a blocking reagent, it can be selected and used from those known as a protective group for a hydroxyl group.

Examples of the blocking reagent include trialkyl-substituted silyl halides such as trimethylsilyl chloride, dimethylisopropylsilyl chloride and t-butyldimethylsilyl chloride. Trimethylsilyl chloride can be preferably used as the blocking reagent.

In this blocking reaction, the treatment can be carried out by adding a blocking reagent to the polysiloxane oligomer product obtained in the first step. The reaction mixture to which the blocking reagent is added is about 5 ° C to about 60 ° C, preferably about 15 ° C.
To about 40 ° C, more preferably about 20 ° C to about 30 ° C
The reaction is carried out for about 5 hours to about 70 hours, preferably for about 10 hours to about 40 hours, and more preferably for about 10 hours to about 20 hours while gently stirring or shaking. The reaction mixture containing the block-treated polysiloxane oligomer product is then subjected to evaporative removal treatment to remove low-boiling substances and solvents, if necessary, to obtain a block-treated polysiloxane oligomer product. You can In this blocking reaction, the organic solvent, water and acid as used in the above-mentioned first step can be appropriately added in order to obtain the desired product.

The block-treated polysiloxane oligomer product thus obtained can then be further reacted with water. In treating the blocked polysiloxane oligomer product, the starting blocked polysiloxane oligomer product is preferably reacted with water in the presence of an organic solvent. The reaction is preferably carried out under acidic conditions. The reaction system can be made acidic by adding an acid. Examples of the acid include inorganic acids such as hydrochloric acid, bromic acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, bisulfate, and acidic sulfite as used in the first step, or salts thereof, acetic acid, butyric acid. ,formic acid,
Organic acids such as oxalic acid, succinic acid, fumaric acid and benzoic acid can be mentioned. Of these, hydrochloric acid can be preferably used.

The organic solvent which can be used in this reaction includes methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol and pentanol as used in the first step. Examples thereof include aliphatic alcohols such as hexanol, heptanol, octanol, and decanol, alicyclic alcohols such as cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, and cycloheptanol, or a mixture thereof. As the organic solvent, methanol, ethanol or the like is preferably used.

In treating the blocked polysiloxane oligomer product, the starting blocked polysiloxane oligomer product is added with an appropriate amount of organic solvent and water, and then the mixture is added with an appropriate amount of acid. With vigorous stirring for about 10 minutes to about 1 hour, preferably about 2
The reaction mixture is allowed to react for 0 to about 40 minutes, more preferably for about 25 to about 35 minutes to form a uniform reaction mixture, and then the homogeneous reaction mixture is about 5 ° C to about 80 ° C, preferably about 15 ° C. To about 50 ° C, more preferably about 20 ° C
From about 5 hours to about 100 hours, preferably from about 10 hours to about 50 hours, while gently stirring or shaking. Further, the reaction may be carried out for about 15 hours to about 30 hours.

In treating the polysiloxane oligomer product, in the case of an organic solvent such as methanol, 1 g of the starting blocked polysiloxane oligomer product is used.
About 0.05g to about 3g, preferably about 0.1g per
To about 1 g, more preferably about 0.2 g to about 0.6
g used. In the treatment of the polysiloxane oligomer product, water is about 0.8 to about 30 times, preferably about 1.0 to about 15 times, more preferably about 1 to about 1 times the starting polysiloxane oligomer product. It is used in an amount of 0.5 to 6 times the molar amount. The amount of acid added in this reaction is, for example, in the case of hydrochloric acid, from about 0.001 g to about 2 g, preferably about 0.005 g per g of starting blocked polysiloxane oligomer product.
To about 1 g, more preferably about 0.01 g to about 0.1 g.
5 g is used. By increasing the amount of acid added in this reaction, a product with a higher number average molecular weight (Mn) can be obtained.

The final polymer product thus obtained can be further treated with a blocking reagent. This treatment can be performed in the same manner as the above blocking reaction. The reaction mixture containing the polymer product thus treated can then be subjected to an evaporation removal treatment to remove low boiling substances and solvents, if necessary, to obtain the desired polymer. As the blocking reagent, phosphoric acid or a phosphoric acid ester may be used to form a polysiloxane oligomer blocked with a phosphoric acid group. In this case, the oligomer product obtained by the hydrolysis reaction under the polycondensation condition of the first step is treated under the hydrolysis condition to form a partially free -Si-OH group in the oligomer product. Let The starting oligomer product is preferably reacted with water in the presence of an organic solvent. The reaction is preferably carried out under acidic conditions.
The reaction system can be made acidic by adding an acid. The acid may be selected from those used in the hydrolysis reaction under the polycondensation conditions in the first step. Of these, hydrochloric acid can be preferably used. The amount of acid used may be a catalytic amount.

The organic solvent used in this reaction may be selected from those used in the hydrolysis reaction under the polycondensation conditions in the first step. As the organic solvent, methanol, ethanol or the like can be preferably used. In this partial hydrolysis reaction, an appropriate amount of organic solvent and water are added to the starting oligomer,
Next, an appropriate amount of acid is added to the mixture, and the mixture is reacted for about 10 minutes to about 2 hours, preferably for about 20 minutes to about 90 minutes, more preferably for about 25 minutes to about 55 minutes to form a uniform reaction mixture. The reaction is usually about 5 ° C to about 8 ° C.
The temperature is kept at 0 ° C., preferably about 15 ° C. to about 50 ° C., more preferably about 20 ° C. to about 40 ° C., with gentle stirring or shaking. Depending on the type of alkoxide group in the silicon alkoxide used, the reaction time also needs to be longer. In general, those having an alcohol residue having a large number of carbon atoms require a long reaction time, but the reaction time can be changed by adjusting the amount and type of coexisting water, organic solvent, and acid.

In this partial hydrolysis reaction, the organic solvent is used in an amount of about 3.0 times mol to about 20 mol per starting oligomer.
Double mole, preferably about 4.5 to about 10 moles,
More preferably, it is used in an amount of about 6.5 times to about 8.5 times the molar amount. During the oligomer hydrolysis reaction, water is about 0.1 times to about 2 times, preferably about 0.15 times to about 1.8 times, more preferably about 0.2 times, the mole of the starting oligomer. To about 1.6 times the molar amount.

Next, the partially hydrolyzed oligomer product thus obtained is treated with phosphoric acid or a phosphoric acid ester to synthesize an oligomer product in which free --Si--OH groups are blocked. The phosphoric acid ester that can be used in this reaction can be selected from those known as phosphoric acid ester, and can be used as long as it is a known reagent or commercially available and easily available as long as it meets such purpose. It can be used by selecting from the reagents that can be used. As such a phosphoric acid ester,
In addition, it can be used by selecting from known ones as a protective group for a hydroxyl group.

Examples of the phosphoric acid ester include mono-, di- or tri-saturated or unsaturated hydrocarbon-substituted phosphoric acid esters, for example, trimethyl phosphoric acid ester, triethyl phosphoric acid ester, dimethylisopropyl phosphoric acid ester, t-. Alkyl-substituted phosphates such as butyl dimethyl phosphate, arylalkyl-substituted phosphates such as tribenzyl phosphate, aryl-substituted phosphates such as triphenyl phosphate, cycloalkyl-substituted phosphates such as tricyclohexyl phosphate Phosphoric acid ester, etc., and these alkyl groups, cycloalkyl groups, aryl groups or aralkyl groups optionally have substituents such as alkyl groups, aryl groups, aralkyl groups, cycloalkyl groups, hydroxyl groups and halogen atoms. Good. As the phosphoric acid ester, trimethyl phosphoric acid ester and triethyl phosphoric acid ester can be preferably used.

In this blocking reaction, the treatment can be carried out by adding phosphoric acid or a phosphoric acid ester to the oligomer product obtained by partial hydrolysis. The reaction mixture to which the phosphoric acid ester has been added is kept at about 5 ° C to about 80 ° C, preferably about 15 ° C to about 40 ° C, more preferably about 20 ° C to about 30 ° C, while gently stirring or shaking. For about 1 hour to about 30 hours, preferably about 2 hours to about 20 hours, more preferably about 3 hours to about 15 hours. The reaction mixture containing the block-processed oligomer product can then be subjected to evaporation removal treatment to remove low-boiling substances and solvents, if necessary, to obtain the block-processed oligomer product. In this blocking reaction, the organic solvent, water and acid used in the above polycondensation or partial hydrolysis step may be appropriately added to obtain the desired product.
The reaction mixture containing the block-treated polymer product thus obtained can then be subjected to an evaporation removal treatment to remove low-boiling substances and solvents, if necessary, to obtain the desired polymer.

The block-treated oligomeric product thus obtained can then be further reacted with water in order to easily form the final polymeric product.
In treating the block-treated oligomer product, the starting blocked oligomer product is preferably reacted with water in the presence of an organic solvent. The reaction is preferably carried out under acidic conditions. The reaction system can be made acidic by adding an acid. Examples of the acid include hydrochloric acid, bromic acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, bisulfate, acidic sulfite and the like inorganic acids or salts thereof, acetic acid used in the above first step. Organic acids such as butyric acid, formic acid, oxalic acid, succinic acid, fumaric acid and benzoic acid can be mentioned. Of these, hydrochloric acid can be preferably used.

The organic solvent used in this reaction can be selected from those used in the above first step. As the organic solvent, methanol, ethanol or the like is preferably used. In the production of the above polysiloxane oligomer, it is possible and preferable to select the conditions for obtaining a structure having a linear structure and further having a unit component linearly connected at least as long as possible in one dimension. .

In the above production method, in the aqueous solution,
A pH buffer, a gelling agent, a coloring agent and the like may be added as long as they meet the purpose of the present invention. The degree of polymerization, properties, etc. of the polysiloxane oligomer formed can also be adjusted by these substances. As the water used,
Purified water, an acidic aqueous solution can be mentioned, but in order to impart the required specific properties to the formed polysiloxane oligomer, a metal, a metal salt, an inorganic compound, an organic compound, or the like is added to purified water.
It is also possible to use a material to which a pigment, a semiconductor material, a drug or the like is added. Purified water is preferably used as the water used, whereby a high-purity polysiloxane oligomer is easily formed.

The inorganic silicic acid polymer molded article obtained in the present invention can be processed into various inorganic functional materials by using a general method widely known in the art. Such products are
It has excellent chemical durability such as acid resistance, water resistance, and alkali resistance, excellent mechanical strength, and can be used for surface processing of materials. The silicic acid polymer obtained in the present invention also gives the possibility to the development of an excellent next-generation concrete having high strength and high durability showing chemical resistance, and an inexpensive cement having excellent workability. Could be used to manufacture.

In recent years, in addition to exhibiting strength and watertightness and chemical resistance to chlorine ions or sulfate ions in seawater or air, it also has high strength and high durability with excellent waterproofness. The development of a technique for producing a cement substitute for giving concrete has been spotlighted as contributing to the development of next-generation concrete, and therefore its development is being actively conducted at present. However, the silicic acid polymer obtained by the present invention is It paves the way for providing concrete with high strength and high durability showing such chemical resistance.

The polysiloxane oligomer used in the present invention is excellent in flexibility and exhibits elastic properties, and other than inorganic fillers such as reactive diatomaceous earth and reactive silica sand of the present invention, for example, Na ₄ SiO ₄ , Na ₂ SiO
₃ · 9H ₂ O, sodium silicates such as Na ₂ SiO ₃ · CaO, react with silicic acid calcium salt, such as CaSiO _3, while there is a higher strength, with a certain and highly durable toughness It is possible to provide concrete that is resistant to cracking. The material thus obtained has excellent properties as a structural material and a structural adhesive.

[0042]

EXAMPLES Next, the present invention will be described more specifically by showing examples, but it is understood that the present invention is not limited to these examples and can be carried out in various forms as long as the idea thereof is followed. Should be.

Example 1 Tetraethoxysilane (special silicon reagent SP) was used to carry out a reaction for forming a silicic acid polymer. (1) Synthesis reaction of polysiloxane oligomer 20 g (1.0 mol) of tetraethoxysilane (TEOS) was placed in an eggplant-shaped flask containing a stirrer, and then 3.09 g (2.0 mol) of methanol and distilled water were added thereto. 2.53
g (1.5 mol) was added, and a 35% strength hydrochloric acid solution 1 was added.
00 mg (0.01 mol) was added. The reaction mixture is allowed to react for about 30 minutes with vigorous stirring. When the reaction mixture becomes uniform, stirring is stopped, and the reaction mixture is placed in a constant temperature vibrating water tank at about 30 ° C. and reacted for about 24 hours while stirring and vibrating.

Trimethylsilyl chloride 1 was added to the reaction mixture containing the polysiloxane oligomer obtained in the above step.
5 g (1.5 mol) is added and reacted for about 12 hours with stirring. The low-boiling substances in the reaction mixture thus obtained are removed by evaporation to obtain a TMS-blocked polysiloxane oligomer as a residue. In order to determine the molecular structure of the obtained polysiloxane oligomer, IR
Spectroscopy was used. The number average molecular weight (Mn) of the obtained polysiloxane oligomer was 1230, and Mw / Mn was 1.49.

(2) Synthesis reaction of polysiloxane oligomer blocked with TMS Using the polysiloxane oligomer blocked with TMS obtained in the above step, a second oligomer formation reaction was carried out. To an aqueous solution containing 3 g of the TMS-blocked polysiloxane oligomer (starting oligomer) obtained above, 1.0 g of methanol and 75 mg of a 35% strength hydrochloric acid solution were added. The reaction mixture is allowed to react for about 30 minutes with vigorous stirring. When the reaction mixture becomes uniform, stirring is stopped, the reaction mixture is placed in a constant temperature vibrating water bath at about 30 ° C., and the reaction is continued for about 20 hours while stirring and vibrating.

Next, 1.5 g of trimethylsilyl chloride (TMSC) is added to the reaction mixture obtained in the above step, and the mixture is reacted for about 12 hours while stirring. The low-boiling substances in the reaction mixture thus obtained are removed by evaporation,
A TMS-blocked second oligomer is obtained as the residue. The above example is referred to as Experimental Example 1. Similarly, Experimental Examples 2 to 3 were performed by changing the amount of the hydrochloric acid solution used. Table 1 shows examples of their formulations.

[0047]

[Table 1]

GPC (gel permeation chromatography) was used to measure the molecular weight and molecular weight distribution of the obtained second oligomer. Table 2 shows a summary of the results obtained in the above examples.

[0049]

[Table 2]

Example 2 20 g (1.0 mol) of tetraethoxysilane (TEOS) was placed in a round-bottomed flask containing a stir bar, and then 3.09 g (2.0 mol) of methanol and distilled water were added thereto. 53
g (1.5 mol) was added, and a 35% strength hydrochloric acid solution 1 was added.
00 mg (0.01 mol) was added. The reaction mixture is allowed to react for about 30 minutes with vigorous stirring. When the reaction mixture becomes uniform, stirring is stopped, and the reaction mixture is placed in a constant temperature vibrating water tank at about 30 ° C. and reacted for about 24 hours while stirring and vibrating.

Trimethylsilyl chloride 1 was added to the polysiloxane oligomer-containing reaction mixture obtained in the above step.
Add 5 g (1.5 mol) and react with stirring.
The low-boiling substances in the reaction mixture thus obtained are removed by evaporation to obtain a TMS-blocked polysiloxane oligomer as a residue. GPC (Gel Permeation Chromatograph) was used to determine the molecular structure of the resulting polysiloxane oligomer. The number average molecular weight (Mn) of the obtained polysiloxane oligomer was 12
30 and Mw / Mn was 1.49.

Example 3 (1) Polysiloxane Oligomer Synthesis Reaction 200 g (10.0 mol) of tetraethoxysilane (TEOS) was placed in a round-bottomed flask equipped with a stir bar, and then 30.9 g of methanol and distilled water were added thereto. 25.3 g (15.
0 mol) was added, and 1.0 g of a 35% strength hydrochloric acid solution was added.
(0.10 mol) was added. The reaction mixture is allowed to react for about 30 minutes with vigorous stirring. When the reaction mixture becomes uniform, stirring is stopped, the reaction mixture is placed in a constant temperature vibrating water bath at about 30 ° C., and the reaction is continued for about 20 hours while stirring and vibrating.

The volatile low-boiling substances and the solvent in the polysiloxane oligomer-containing reaction mixture obtained in the above step were removed by evaporation, and polytetraethoxysilane (PTEOS) was used as a residue as a transparent viscous liquid. obtain.
The properties of the PTEOS polysiloxane oligomer obtained in the above step were measured by GPC (gel permeation chromatograph) using an oligomer blocked with trimethylsilyl chloride. Table 3 summarizes the blending ratios of the reagents used and the reaction times, and also shows the properties of PTEOS.

[0054]

[Table 3]

(2) Phosphoric Acid Group Blocking Reaction of Polysiloxane Oligomer Distilled water and a catalytic amount of 1N hydrochloric acid are added to the polysiloxane oligomer-containing ethanol solution (using 99.5% ethanol) obtained in the above step (1). In addition, the mixture thus obtained is allowed to react for 45 minutes with stirring at room temperature. To the partially hydrolyzed polysiloxane oligomer-containing reaction mixture thus obtained, triethyl phosphate (special grade reagent) is added and reacted at 80 ° C. for about 15 hours with stirring. Volatile low-boiling substances and solvents in the blocked polysiloxane oligomer-containing reaction mixture obtained in the above step were removed by evaporation, and the residue was blocked with phosphoric acid groups as a colorless transparent viscous liquid. Obtain polytetraethoxysilane (PTEOS).
Table 4 shows the blending ratio of the reagents used and the yield of the product.

[0056]

[Table 4]

Example 4 (1) Polysiloxane oligomer synthesis reaction Tetraethoxysilane (TEOS) was placed in a round-bottomed flask equipped with a stir bar, then methanol and distilled water were added thereto, and a 35% hydrochloric acid solution was further added. Was added. The reaction mixture is allowed to react for about 30 minutes with vigorous stirring. When the reaction mixture becomes uniform, stop stirring, and allow to react for about 24 hours while stirring at room temperature. Table 5 shows the mixing ratios of the reagents used and the reaction conditions.

[0058]

[Table 5]

The volatile low-boiling substances and the solvent in the polysiloxane oligomer-containing reaction mixture obtained in the above step were removed by evaporation, and polytetraethoxysilane (PTEOS) was used as a transparent and viscous liquid as a residue. obtain.
The properties of the PTEOS polysiloxane oligomer obtained in the above step were measured by GPC (gel permeation chromatograph) using an oligomer blocked with trimethylsilyl chloride. Table 6 shows the proportion of water used and the properties of the PTEOS oligomer.

[0060]

[Table 6]

(2) Phosphoric Acid Group Blocking Reaction of Polysiloxane Oligomer Distilled water and a catalytic amount of 1N hydrochloric acid are added to the polysiloxane oligomer-containing ethanol solution (using 99.5% ethanol) obtained in the above step (1). In addition, the mixture thus obtained is allowed to react for 45 minutes with stirring at room temperature. To the partially hydrolyzed polysiloxane oligomer-containing reaction mixture thus obtained, triethyl phosphate (special grade reagent) is added and reacted at 80 ° C. for about 3 hours with stirring. Volatile low-boiling substances and solvents in the blocked polysiloxane oligomer-containing reaction mixture obtained in the above step were removed by evaporation under reduced pressure with a vacuum pump in a water bath at 80 ° C., and the residue was colorless and transparent. As a viscous liquid, phosphoric acid group-blocked polytetraethoxysilane (PTEOS) is obtained. Table 7 shows the mixing ratio of the reagents used.

[0062]

[Table 7]

Example 5 As an inorganic filler, diatomaceous earth and silica sand were used, and 4 g of silicon tetrachloride was used for 1 g of each and 4 g for diatomaceous earth and 1 g for silica sand. The silica sand used was Toyoura standard sand, Yamagata prefecture Iide, Yamagata prefecture Mogami, Aichi prefecture Seto, and Gifu prefecture Mizunami. The container containing the reaction mixture was irradiated with ultrasonic waves for about 30 minutes, and then unreacted silicon tetrachloride was removed under reduced pressure in a vacuum. Ammonia gas was passed through the thus obtained silicon tetrachloride-treated diatomaceous earth and silica sand for about 30 minutes to carry out a reaction. Next, the reactive diatomaceous earth and silica sand thus obtained were reacted with the polysiloxane oligomer of Experimental Example 3 obtained in Example 1 (2).

Example 6 Using diatomaceous earth and silica sand as inorganic fillers, 10 ml of 35% hydrochloric acid was added to 10 g of each, reacted at about 100 ° C. or room temperature for about 6 hours, washed with water, and then vacuum dried. . The silica sand used was Toyoura standard sand, Yamagata prefecture Iide, Yamagata prefecture Mogami, Aichi prefecture Seto, and Gifu prefecture Mizunami.
Next, the reactive diatomaceous earth and silica sand thus obtained were reacted with the polysiloxane oligomer of Experimental Example 3 obtained in Example 1 (2).

Example 7 Using diatomaceous earth and silica sand as inorganic fillers, 10 ml of an aqueous sodium hydroxide solution was added to 10 g of each,
After reacting for about 20 hours at room temperature, wash with water and then 35
% Hydrochloric acid was added for neutralization, washing with water, and then vacuum drying. Vacuum dried. The silica sand used was Toyoura standard sand, Yamagata prefecture Iide, Yamagata prefecture Mogami, Aichi prefecture Seto, and Gifu prefecture Mizunami. Next, the reactive diatomaceous earth and silica sand thus obtained were reacted with the polysiloxane oligomer of Experimental Example 3 obtained in Example 1 (2). Table 8 shows a summary of the curing reaction results of the polysiloxane oligomers of Examples 5, 6 and 7 and the surface-treated filler.

[0066]

[Table 8]

While the untreated diatomaceous earth and silica sand did not react with the oligomer and did not harden, after the treatment by the method of Example 5, all reacted and hardened promptly. It was confirmed that this method is effective in increasing the surface activity of the inorganic filler. The estimated reaction mechanism is as shown in FIG. Regarding the curing reaction results of the polysiloxane oligomers of Examples 6 and 7 and the surface-actively treated filler,
Quantification of OH groups on the surface of silica sand was performed by IR spectroscopy. K
It was measured using only silica sand to avoid the influence of water in Br. Polyphenylene acetylene was used as an internal standard. Fig. 2 shows I of silica sand (Toyoura standard sand) before and after treatment.
The measurement results of the R spectrum are shown. The sharp absorption around 3000 cm ^-1 is the absorption of CH stretching vibration of the benzene ring of polyphenylene acetylene, and the wide absorption of 3300 cm ^{-1 is} the absorption of stretching vibration of SiOH. The change in the amount of SiOH can be calculated from the area ratio of these two absorptions, and the results are shown in Table 9.

[0068]

[Table 9]

As a result, it can be seen that the treatment with HCl and NaOH increases the OH groups on the silica sand surface. HC
In the case of 1, the amount of OH groups depends on the treatment temperature, and it was found that the amount of OH groups was large at 100 ° C. In the case of NaOH treatment, the number of OH groups was the largest at 10 M, depending on the concentration of NaOH, and the increase in OH groups tended to decrease as the concentration was increased.

FIG. 3 shows the IR spectrum of silica sand in each production area. Sharp absorption was also observed in addition to the absorption of broad OH groups near 3300 cm ^-1 . This is due to the absorption of MOH by metals other than SiOH, and it was considered necessary to understand this as a factor affecting the condensation reaction with the oligomer. That is, from the IR spectrum of FIG.
Information on the presence of OH groups as well as the amount of H groups present was also obtained. From the above, by treatment with HCl and NaOH, the amount of OH groups on the silica sand surface was
Up to 1.30 times with HCl and 1.45 with NaOH
I was able to double it.

(3) PTEO blocked with a phosphate group
Hydrolysis treatment of S oligomer 1N hydrochloric acid was added to the PTEOS oligomer blocked with a phosphate group obtained in the step of Example 4 (2) above, and the mixture was stirred and mixed until it became transparent. 1N hydrochloric acid has a weight ratio of 0.
32, 0.34, 0.36 and 0.40 were used. The product can be reacted and solidified with the reactive inorganic fillers obtained in Examples 5, 6 and 7. When a polytetraethoxysilane (PTEOS) oligomer having a relatively wide molecular weight distribution is used, one having a large compressive strength is obtained. Further, when a PTEOS oligomer having a large average molecular weight is used, one having a large compressive strength can be obtained. When the degree of blocking by the phosphoric acid ester is relatively low, the one having higher compressive strength can be obtained.

[0072]

EFFECTS OF THE INVENTION According to the present invention, the reactivity of the surface of the inorganic filler can be enhanced, and the treatment is carried out by a simple method, for example, one or more treating agents selected from silicon tetrachloride, ammonium acid and base. As a result, the amount of active groups on the filler surface can be increased. By using these inorganic fillers, it is effective for highly strengthening the structure and imparting toughness. According to the present invention, it is possible to synthesize an inorganic silicic acid polymer molded product by reacting a more linear polysiloxane oligomer with an inorganic filler that has strength in the material itself and is stable once it is a molded product. Thus, an inorganic material having a flexible structure can be obtained. In the method for producing an inorganic silicic acid polymer of the present invention, the quality can be controlled by a simple control operation.

[Brief description of drawings]

FIG. 1 presumably shows a formation scheme of a reactive inorganic filler and a reaction scheme with a polysiloxane oligomer in the treatment according to the present invention.

FIG. 2 shows a change in IR spectrum of Toyoura standard sand silica sand treated with hydrochloric acid or sodium hydroxide according to the present invention.

FIG. 3 shows IR spectra of various silica sands.

Claims (21)

[Claims] 1. Reactivity characterized by being obtained by treating a silicic acid-containing inorganic filler with an activation-imparting agent and then reacting it with ammonia or an amine compound, or by treating it with an acid or a base. Inorganic filler. 2. The reactive inorganic filler according to claim 1, wherein the silicic acid-containing inorganic filler is selected from the group consisting of diatomaceous earth, silica sand, silicic acid-containing volcanic ash, fly ash, silica rock, and quartz. 3. The reactive inorganic filler according to claim 1, wherein the silicic acid-containing inorganic filler is diatomaceous earth or silica sand. 4. The reactive inorganic filler according to claim 1, wherein the activation imparting agent is a silicon halide. 5. The reactive inorganic filler according to claim 1, wherein the activation imparting agent is silicon tetrachloride. 6. A method of reacting a silicic acid-containing inorganic filler treated with an activator with ammonia.
The reactive inorganic filler according to any one of 1 to 4. 7. An inorganic filler containing silicic acid is added to hydrochloric acid, bromic acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, peroxosulfuric acid,
The reactive inorganic filler according to claim 1, which is to be reacted with a material selected from the group consisting of chromic acid, permanganic acid and trifluoroacetic acid. 8. A silicic acid-containing inorganic filler is reacted with one selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide and barium hydroxide, and then hydrochloric acid, bromic acid, Sulfuric acid, nitric acid, phosphoric acid,
The reactive inorganic filler according to claim 1, which is neutralized with a material selected from the group consisting of perchloric acid, peroxosulfuric acid, chromic acid, permanganic acid and trifluoroacetic acid. 9. A method for producing a reactive inorganic filler, which comprises treating a silicic acid-containing inorganic filler with an activation-imparting agent and then reacting it with an ammonia or an amine compound, or by treating it with an acid or a base. 10. A product obtained by reacting the reactive inorganic filler according to claim 1 with a polysiloxane oligomer blocked with a trialkylsilyl group or phosphoric acid or a phosphoric acid ester group. Characteristic molded inorganic silicate polymer. 11. A polysiloxane oligomer blocked with a trialkylsilyl group is hydrolyzed with a silicon alkoxide under polycondensation conditions, and the resulting silicic acid polycondensate is composed of a trialkylsilyl halide at least once. The molded inorganic silicate polymer according to claim 10, which is obtained by treating with a blocking reagent. 12. The polysiloxane oligomer blocked with a trialkylsilyl group used is obtained by partially preliminarily carrying out a hydrolysis treatment.
The inorganic silicic acid polymer molded article according to 1. 13. A polysiloxane oligomer blocked with phosphoric acid or phosphoric acid ester groups is represented by the general formula: (In the formula, i is 1 to 20, m is 0 to 20, R may be the same or different, and is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 1 to 10 carbon atoms, or -Si. (OR) ₃
Or —PO (OR ¹ ) ₂ and at least one of R is —PO (OR ¹ ) ₂ and R ¹ may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon atom. Number 1
10 to 10 aralkyl groups, —PO (OR ¹ ) ₂ or —Si
The molded inorganic silicate polymer according to claim 10, which is a silicic acid ester represented by (OR) ₃ . 14. A polysiloxane oligomer blocked with a phosphoric acid or a phosphoric acid ester group is hydrolyzed with a silicon alkoxide under polycondensation reaction conditions to form a silicic acid polycondensed oligomer, and then the obtained silicic acid is obtained. A partially hydrolyzed silicic acid polycondensation oligomer product obtained by partially hydrolyzing an acid polycondensation oligomer product is obtained by blocking treatment with phosphoric acid or phosphoric acid ester at least once. Item 10. An inorganic silicic acid polymer molded article according to item 10. 15. The silicic acid oligomer blocked with a phosphoric acid or phosphoric acid ester group has a number average molecular weight of 1 or less.
The molded product of inorganic silicic acid polymer according to claim 14, which is an oligomer having a weight average molecular weight / number average molecular weight ratio of 1.2 or more. 16. The molded inorganic silicic acid polymer according to claim 13, wherein the phosphoric acid ester is a monoalkyl phosphoric acid ester, a dialkyl phosphoric acid ester, or a trialkyl phosphoric acid ester. 17. The trialkyl phosphate ester is trimethyl phosphate ester, triethyl phosphate ester, tri-n-propyl phosphate ester, triisopropyl phosphate ester, tri-n-butyl phosphate ester, or tri-t-ester. The inorganic silicic acid polymer molded article according to claim 16, which is one of trialkyl phosphates selected from the group consisting of butyl phosphates. 18. Tetraethoxysilane is subjected to a polycondensation reaction in the presence of water, a strong acid and a lower alcohol at about 20 to 40 ° C. for about 15 to 30 hours, and the resulting silicic acid polycondensate is partially hydrolyzed under hydrolysis conditions. After that, the resulting partially hydrolyzed silicic acid polycondensate is reacted with a tri-lower-alkyl-substituted phosphoric acid ester, and then the resulting phosphoric acid group-blocked silicic acid oligomer is hydrolyzed in the presence of an acid. The molded product of an inorganic silicic acid polymer according to claim 10, wherein the obtained product is reacted with the reactive inorganic filler according to any one of claims 1 to 8 and solidified. 19. Tetraethoxysilane in an amount of about 1.2 to 1.8 moles water per about 1.0 mole tetraethoxysilane, about 0.005 to 0.02 moles concentrated hydrochloric acid and about 1.2 moles.
After the polycondensation reaction is performed at about 20 to 40 ° C. for about 15 to 30 hours in the presence of ˜1.8 mol of a lower alcohol, the obtained silicic acid polycondensate is partially reacted under hydrolysis conditions, and then the partial hydrolysis is obtained. About 1.0 mol of silicic acid polycondensate to about 0.4 to 3.0
The product obtained by reacting with a molar amount of a tri-lower alkyl-substituted phosphoric acid ester, and then treating the obtained phosphoric acid group-blocked silicic acid oligomer with an aqueous hydrochloric acid solution. 11. The inorganic silicic acid polymer molded article according to claim 10, which is made to react with the reactive inorganic filler as described above and solidify. 20. The reactive inorganic filler according to claim 1 is reacted with a polysiloxane oligomer blocked with a trialkylsilyl group or a phosphoric acid or a phosphoric acid ester group. Method for producing molded inorganic silicic acid polymer. 21. Surface-Si of a silicic acid-containing inorganic filler
A reactive inorganic filler characterized by being subjected to a treatment for increasing —OH groups.