JPH07292118A - Production of inorganic silicic acid polymer - Google Patents

Abstract

PURPOSE:To obtain a new polymer having a high degree of linear structure and capable of giving an inorganic material excellent in flexibility, etc., by hydrolyzing a silicon alkoxide and treating the obtained silicic acid polycondensate with phosphoric acid (ester). CONSTITUTION:This silicic acid polymer is obtained by hydrolyzing a silicon alkoxide in which silicon is bound with plural alkoxides to obtain a linear or monocyclic silicic acid polycondensate, optionally further hydrolyzing the obtained silicic acid polycondensate and subsequently treating the product with a linear, cyclic or network polyphosphoric acid or mono-, di-, or tri-hydrocarbon substituted phosphoric acid ester once or more than one time. The silicic acid polymer is expressed by formula I [i=1-20; m=0-200 R is H, a 1-6C alkyl, etc.], having a number-average molecular weight of >=1000. Further, the silicic acid polymer is blocked with a phosphoric acid (ester) consisting of an oligomer whose having a weight-average molecular weight/number-average molecular weight ratio of >=1.2. The silicic acid esters of formulae II to V, etc., are examples of the polymer.

Description

Detailed Description of the Invention

[Detailed Description of the Invention]

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a novel inorganic silicic acid polymer having a highly linear structure (including a terminally condensed monocyclic structure). The present invention particularly relates to a method for producing a silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group, and further solidifying the silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group under hydrolysis conditions. Also provided is a method for producing an inorganic molded silicic acid polymer characterized by the above.

The present invention also hydrolyzes a silicon alkoxide, particularly under polycondensation conditions,
In forming a silicic acid polymer, partially reacting a silicon alkoxide to form a silicic acid partial polycondensate, and then subjecting the obtained product to at least one blocking treatment with phosphoric acid or a phosphoric acid ester. In particular, the phosphoric acid or phosphorus characterized in that the product obtained is partially hydrolyzed and then the product obtained is subjected to a blocking treatment with phosphoric acid or a phosphoric acid ester at least once. The present invention relates to a method for producing a silicic acid polymer blocked with an acid ester group, and further, the phosphoric acid thus obtained or the silicic acid polymer blocked with a phosphoric acid ester group is further hydrolyzed to give silicic acid. It also relates to forming a gel or sol. In particular, the present invention is to provide an inorganic material product having a very high strength and yet being flexible.

[0003]

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 also has radiation resistance, its hardness is high and it is abrasion resistant. Such inorganic material substances also have oil resistance and solvent resistance,
Utilizing these characteristics, heat resistant materials, non-combustible materials, heat ray reflective materials, electrical insulating materials, transparent conductive materials, anticorrosive materials, chemical resistance imparting materials, surface protective materials with abrasion resistance, antireflection and lubrication effects It is expected to be used as a special functional material having

The utilization development of these inorganic material substances making the most of their characteristics is currently under way.
These inorganic material substances are also promising as new cement substitute materials. 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 to form solid glass or ceramics. This is generally called the sol-gel method.

However, for example, an inorganic material obtained by subjecting a metal alkoxide such as tetraethoxysilane [Si (OEt) ₄ , TEOS] to hydrolysis treatment in a usual manner results in three-dimensional polymerization, The product obtained has the disadvantage of being brittle. The hydrolysis reaction of tetraethoxysilane is shown in the following formula.

[0006]

[Chemical 3]

The glass, ceramics, etc. obtained by utilizing such a conventional method have a three-dimensional three-dimensional structure and have become hard and brittle as described above. This has been a major problem when used as a cement substitute material.

In order to solve the above-mentioned problems, the inventors of the present invention produce a material of an inorganic material by polymerizing a metal alkoxide having many functional groups such as silicon alkoxide. I think that if the structure of is linear, that is, if the unit components are one-dimensionally long and linearly connected, it may have flexibility and elasticity like an organic polymer. , And conducted intensive research to produce an inorganic material having such a structure.

Regarding the control of the structure of the product of the inorganic material having the Si—O—Si bond obtained by using the Si—O skeleton forming raw material such as tetraethoxysilane which is one of the metal alkoxides. However, the control of the structure of the inorganic product in the polymerization reaction of metal alkoxides with four functional groups such as tetraethoxysilane is not possible due to the fact that it has many functional groups. Therefore, there are many problems in making the polymer. Actually, when polymerizing this tetraethoxysilane as a starting material, the reaction is controlled by adjusting the catalyst and usually adjusting the pH with an acid or an alkali. From the viewpoint of ease of use, it is necessary to raise the pH, but if the pH is too high, it becomes difficult to obtain a three-dimensional three-dimensional structure, and it is difficult to obtain the desired structure. Couldn't even get.

[0010]

Means for Solving the Problems In producing an inorganic material substance by polymerizing a metal alkoxide having many functional groups such as a silicon alkoxide, the inventors of the present invention have a linear structure. As a result of earnest research to produce a substance, that is, an inorganic material substance having a structure in which unit components are linearly connected as long as possible in one dimension as much as possible, a uniform and reproducible linear structure is obtained by a simple method. We succeeded in producing an inorganic material with

[0011]

[Chemical 4]

Based on this result, the present inventors tried to produce an inorganic material substance containing an inorganic material only by using an inorganic blocking agent and using an inexpensive material, and the present invention was obtained. completed. This method is expressed by the following formula.

[0013]

[Chemical 5] In the above formula, n is an integer of 1 or more, preferably 1 to 30, and m
Is an integer of 0 or more, preferably 0 to 20.

In the present invention, the silicon alkoxide is first hydrolyzed to form a silicic acid polycondensate. This reaction can be carried out under polycondensation conditions, but it is preferred to partially react the silicon alkoxide with water to obtain a partially condensed silicic acid polymer. Particularly, 2 to 30 silicon-containing polycondensates having a linearly long linear structure or a cyclic structure having a linear structure bonded at the end 2
It is preferable to carry out so as to contain a large amount of ˜40 silicon-containing polycondensate. The obtained product can be used after separating it into a single component, but usually, the obtained product may be directly subjected to the next reaction. Next, the obtained silicic acid polycondensation product is treated at least once with phosphoric acid or a phosphoric acid ester to produce a silicic acid polymer blocked with phosphoric acid or a phosphoric acid ester group. The silicic acid polycondensation product is preferably treated so as to be easily partially hydrolyzed and blocked with phosphoric acid or a phosphoric ester group, but when treated with phosphoric acid or a phosphoric ester. At the same time, these conditions can be achieved.

Thus, in the present invention, the silicon alkoxide is hydrolyzed to form a silicic acid polycondensate,
Next, there is provided a method for producing a silicic acid polymer blocked with phosphoric acid or a phosphoric acid ester group, which comprises treating the obtained silicic acid polycondensation product with phosphoric acid or a phosphoric acid ester at least once. is doing. In the present invention, the silicic acid polycondensation product may be treated with phosphoric acid or a phosphoric acid ester once or more than once, and in the case of a plurality of treatments, phosphoric acid or a phosphoric acid ester is treated. The group-blocked silicic acid polymer products can each be treated with phosphoric acid or a phosphoric acid ester, optionally with partial hydrolysis treatment. Furthermore, the silicic acid polymer blocked by the phosphoric acid or phosphoric acid ester group obtained by the production method is solidified under hydrolysis conditions to form an inorganic molded silicic acid polymer, particularly phosphoric acid or It is possible to produce silicic acid polymers that are blocked with phosphate groups. Thus, the present invention provides a method for producing an inorganic molded silicic acid polymer. The thus obtained phosphoric acid or a phosphoric acid ester group-blocked silicic acid polymer has a relatively linear structure and is solidified only by partial hydrolysis treatment, and has excellent flexibility and elasticity. It gives a tough inorganic material having various properties, high strength and high durability. Here, it is needless to say that the term “linear” includes a case where the functional groups are combined with each other to form a monocycle. According to the present invention, the inorganic silicic acid polymer thus obtained is used to provide a route to provide inorganic material products such as mortar and concrete.

The silicon alkoxide has at least one alkoxy group 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 molecular weight 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. As these low molecular weight condensates, linear condensates are preferably used. Further, those having a ring shape by being bonded at the end portion can also be preferably used.

Taking tetraethoxysilane (TEOS) as a reference, the synthesis of linear or cyclic polysiloxanes will be described in particular. First, since tetraethoxysilane has four functional groups, it is necessary to form a difunctional one in order to obtain a linear polysiloxane oligomer. In the present invention, first, a silicon alkoxide is partially reacted with water, and particularly, it is partially reacted with water under polycondensation conditions to synthesize an oligomer (pre-oligomer). It is preferable to mainly synthesize a linear pre-oligomer. Further, those having a ring shape by being bonded at the end portion can also be preferably used. In synthesizing this oligomer (pre-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. Acids include hydrochloric acid, bromic acid,
Inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, perchloric acid, bisulfate, and acidic sulfite, or salts thereof, organic acids such as acetic acid, butyric acid, formic acid, oxalic acid, succinic acid, fumaric acid, and benzoic acid. To be Of these, hydrochloric acid can be preferably used.

As the organic solvent which can be used in this reaction, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 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 reaction for synthesizing this oligomer (pre-oligomer), an appropriate amount of organic solvent and water are added to the starting silicon alkoxide, then an appropriate amount of acid is added to the mixture, and the mixture is stirred vigorously for about 10 minutes. To about 1 hour, preferably about 20 minutes to about 40 minutes, more preferably about 25 minutes to about 35 minutes to form a uniform reaction mixture, and then the homogeneous reaction mixture is mixed from about 0 ° C to about 8
Keeping at 0 ° C., preferably about 0 ° C. to about 50 ° C., more preferably about 0 ° C. to about 40 ° C., with gentle stirring or shaking, for about 1 hour to about 100 hours, preferably about 1 hour to about 50. The reaction is conducted for about 1 hour to about 30 hours, more preferably about 1 hour. Depending on the type of alkoxide group in the silicon alkoxide used, the reaction time also needs to be longer. In general, the one having an alcohol residue having a large number of carbon atoms takes a long time for the reaction, but it can be changed by adjusting the amount and kind of coexisting water, organic solvent and acid.

In the reaction for synthesizing the oligomer (pre-oligomer), the organic solvent is used in an amount of about 0 to about 10 times, preferably about 0.2 times, the mole of the starting silicon alkoxide.
The molar amount is about 5 times to about 5 times, more preferably about 0.5 times to about 2.0 times. During the oligomer (pre-oligomer) synthesis reaction, water is about 0.5 times to about 10 times, preferably about 1.0 times to about 5 times, and more preferably about 1.2 times the starting silicon alkoxide. It is used in an amount of double to about 1.8 times. The amount of acid added in this reaction is from about 0.001 fold to about 4 fold moles, preferably about 0.
002-fold mole to about 1-fold mole, more preferably about 0.
It is used in an amount of 005 times to about 0.02 times.

Next, in the present invention, the oligomer (pre-oligomer) product thus obtained, in particular the linear or cyclic oligomer product, is treated with phosphoric acid or a phosphoric acid ester to obtain a block-treated pre-oligomer. The product is synthesized. The phosphoric acid or phosphoric acid ester that can be used in this reaction can be selected from those known as phosphoric acid or phosphoric acid ester, and can be used as long as it is a known reagent or a commercially available reagent as long as it meets such purposes. It is possible to select and use from among the reagents that have been prepared and are easily available. As such phosphoric acid or phosphoric acid ester, it is possible to select and use from among those known as a protective group for a hydroxyl group.

Prior to treating the above oligomer (pre-oligomer) product, especially the linear or cyclic oligomer product, with phosphoric acid or a phosphoric acid ester, in the present invention, preferably the obtained linear or cyclic oligomer product is obtained. The product is treated under hydrolytic conditions to partially form -Si-OH groups in its linear or cyclic oligomer product. The starting linear or cyclic 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. As the acid, hydrochloric acid, bromic acid, sulfuric acid, nitric acid,
Examples thereof include inorganic acids such as phosphoric acid, perchloric acid, bisulfate, and acidic sulfite, or salts thereof, and organic acids such as acetic acid, butyric acid, formic acid, oxalic acid, succinic acid, fumaric acid, and benzoic acid. Of these, hydrochloric acid can be preferably used. The amount of acid used may be a catalytic amount.

As the organic solvent which can be used in this reaction, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 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 this partial hydrolysis reaction, an appropriate amount of organic solvent and water are added to the starting oligomer, then an appropriate amount of acid is added to the mixture, and the mixture is added for about 10 minutes to about 2 hours.
The reaction is preferably carried out for about 20 minutes to about 90 minutes, more preferably for about 25 minutes to about 55 minutes to obtain a uniform reaction mixture. The reaction is usually about 0 ° C to about 80 ° C, preferably about 0 ° C to about 50 ° C, more preferably about 0 ° 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. Generally, the one having an alcohol residue having a large number of carbon atoms takes a long time for the reaction, but it can be changed by adjusting the amount and kind of coexisting water, organic solvent and acid.

In this partial hydrolysis reaction, the organic solvent is used in an amount of about 0 to about 20 times, preferably about 1 to about 10 times, and more preferably about 2 to about 4 times the starting oligomer. Used in moles. During the oligomer hydrolysis reaction, water is about 0.1 times to about 3 times, preferably about 0.15 times to about 2.5 times, more preferably about 0.2 times, the mole of the starting oligomer. To about 2.0 times the molar amount.

In the present invention, the linear or cyclic partially hydrolyzed oligomer product thus obtained is treated with phosphoric acid or a phosphoric acid ester, and a linear or cyclic oligomer in which the -Si-OH group is blocked is treated. The product can be synthesized. As phosphoric acid, orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, chain polyphosphoric acid such as tetraphosphoric acid,
Examples thereof include those selected from the group consisting of cyclic polyphosphoric acid such as trimetaphosphoric acid and tetrametaphosphoric acid, and network polyphosphoric acid. Examples of the phosphoric acid ester include mono-, di- or tri-saturated or unsaturated hydrocarbon-substituted phosphoric acid ester, and examples thereof include trimethyl phosphoric acid ester, triethyl phosphoric acid ester, dimethylisopropyl phosphoric acid ester, t-butyldimethylphosphoric acid ester. Alkyl-substituted phosphates such as acid esters, aryl-alkyl-substituted phosphates such as tribenzyl phosphate, aryl-substituted phosphates such as triphenyl phosphate, cycloalkyl-substituted phosphates such as tricyclohexyl phosphate And the like. These alkyl groups, cycloalkyl groups, aryl groups or aralkyl groups may optionally have substituents such as alkyl groups, aryl groups, aralkyl groups, cycloalkyl groups, hydroxyl groups and halogen atoms. 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 phosphoric acid ester to the pre-oligomer product obtained in the first step. Further, this blocking reaction can be carried out by adding phosphoric acid or a phosphoric acid ester to the linear or cyclic oligomer product obtained by partial hydrolysis. The reaction mixture to which phosphoric acid or phosphoric acid ester is added is about 5 ° C to about 120 ° C, preferably about 15 ° C to about 100 ° C, more preferably about 2 ° C.
Keeping the temperature at 0 ° C to about 80 ° C, gently stirring or shaking for about 1 hour to about 70 hours, preferably about 2 hours to about 40 hours, more preferably about 2 hours to about 1 hour.
React for 0 hours. The reaction mixture containing the thus-blocked oligomer product, particularly the linear or cyclic oligomer product, is then subjected to an evaporation removal treatment to remove low-boiling substances and a solvent, if necessary, and then blocked. It is possible to obtain oligomeric (pre-oligomeric) products, especially linear or monocyclic oligomeric products.

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. In the present invention, the reaction mixture containing the block-treated pre-oligomer product thus obtained is then subjected to an evaporation removal treatment to remove low-boiling substances and solvents, if necessary, to obtain the desired pre-oligomer product. Can be obtained. In the present invention, a hydrolysis treatment can be performed in order to form a polymer product from the block-treated pre-oligomer product thus obtained. Also, in the present invention, the block-treated oligomer product thus obtained can be solidified under hydrolysis conditions to form the final polymer product. In treating the blocked oligomeric product, the starting blocked oligomeric product is preferably reacted with water 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, and the like used in the first step.
Examples thereof include inorganic acids such as acidic sulfites or salts thereof, and organic acids such as acetic acid, butyric acid, formic acid, oxalic acid, succinic acid, fumaric acid and benzoic acid. Of these, hydrochloric acid can be preferably used. It is also possible to react in an organic solvent.

As the organic solvent which can be used in this reaction, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, pentanol as used in the above first step can be used. 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 the present invention, in the above-mentioned production method, a pH buffering agent, a gelling agent, a coloring agent and the like may be added to the aqueous solution as long as it meets the purpose of the present invention.
The degree of polymerization, properties, etc. of the formed silicic acid polymer can also be adjusted by these substances. As the water used,
Examples include purified water and acidic aqueous solutions. Metals, metal salts, inorganic compounds, organic compounds, pigments, semiconductor materials, chemicals, etc. are added to purified water in order to impart the required specific properties to the formed silicic acid polymer. It is also possible to use the one to which is added.
Purified water is preferably used as the water used, whereby a high-purity silicic acid polymer is easily formed. When the steps according to the steps according to the present invention are carried out, for example, when tetraethylsilane (TEOS) is used as a raw material and triethyl phosphate is used as the phosphate, a compound having a structure represented by the following formula is typically used. can get.

[0031]

[Chemical 6]

(In the formula, i is an integer of 1 or more, preferably 1
~ 20, m is an integer of 0 or more, preferably 0-20,
R can be the same or different, a hydrogen atom, an organic group, preferably an alkyl group having 1 to 6 carbon atoms, or an inorganic base, preferably -Si (OR) ₃ or -PO (OR ¹⁾ _2, wherein R At least one of them is —PO (OR ¹ ) ₂ and R ¹
May be the same or different and is a hydrogen atom, an organic group, preferably an alkyl group having 1 to 6 carbon atoms, or an inorganic group, preferably -PO (OR ¹ ) ₂ or -Si (OR) _3. The final inorganic silicic acid polymer obtained from the phosphoric acid ester-blocked silicic acid oligomer obtained in the above has excellent flexibility and elastic properties, and is applied to the surface of a metal or the like. After drying or heat treatment, a very strong and flexible polymer film of inorganic silicic acid is formed. It can also be used for ceramics production. The thickness, properties and the like of the silicic acid polymer thus formed are appropriately determined in consideration of the properties and the like of the silicic acid polymer to be used according to the purpose of use.

The silicic acid polymer obtained according to the present invention can be processed into various inorganic functional materials by using a general method widely known in the art. Such products have excellent chemical durability such as acid resistance, water resistance, and alkali resistance, and also have excellent mechanical strength, are used for surface processing of materials, and are used for adjusting reflectance and coloring. It can also be used to adjust the electrical conductivity.

The silicic acid polymer obtained in the present invention is also an excellent inorganic adhesive having high strength and high durability showing chemical resistance, which gives the possibility to the development of next-generation concrete and is inexpensive. It can be used to produce cement products with good workability.

In recent years, in addition to exhibiting strength and watertightness, showing chemical resistance to chlorine ions or sulfate ions in seawater or air, it has high strength and high durability excellent in waterproofness. The development of a technique for producing a hydraulic cement composition that gives mortar or concrete has been highlighted as a contribution to the development of next-generation concrete, and therefore its development is currently being actively conducted. Polymers open the way for applications in providing new structural materials (such as mortar or concrete) with high strength and high durability that exhibit such chemical resistance.

The silicic acid polymer obtained in the present invention has excellent flexibility and elastic properties, and is an inorganic filler (filler).
It is possible to give concrete that has higher strength, toughness and high durability, and is resistant to cracking by reacting with. The material thus obtained has excellent properties as a structural material and a structural adhesive.

According to the present invention, the following modes for carrying out the invention are further mentioned. 1. Phosphoric acid characterized by hydrolyzing silicon alkoxide to form a silicic acid polycondensate, and then treating the resulting silicic acid polycondensate product at least once with phosphoric acid or phosphoric acid ester. A silicic acid polymer blocked with a phosphate ester group.

2. The phosphoric acid or phosphate ester group according to item 1, wherein the silicic acid polycondensate product formed by hydrolyzing the silicon alkoxide is a linear silicic acid polycondensate or a monocyclic silicic acid polycondensate. Silicic acid polymer blocked with. 3. The silicic acid polymer blocked with a phosphoric acid or phosphoric acid ester group is an oligomer having a number average molecular weight range of 1000 or more and a weight average molecular weight / number average molecular weight ratio range of 1.2 or more. Or a silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group according to 2. 4. A silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group has the general formula

[0039]

[Chemical 7]

(Wherein i is 1 to 20 and m is 0 to 20)
And R may be the same or different, and is a hydrogen atom or a carbon number 1
~ 6 alkyl group, -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 is a hydrogen atom,
An alkyl group having 1 to 6 carbon atoms, -PO (OR ¹ ) ₂ or-
The silicic acid polymer according to item 1, which is a silicic acid ester represented by Si (OR) ₃ . 5. A silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group has the following formula

[0041]

[Chemical 8]

The silicic acid polymer according to item 1 or 4 above, which is selected from the group consisting of silicic acid esters represented by: 6. The silicon alkoxide is hydrolyzed under polycondensation conditions to form a silicic acid polycondensate, and the resulting silicic acid polycondensate product is subjected to a partial hydrolysis reaction treatment at least once with phosphoric acid or a phosphoric acid ester. The silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group according to item 1 above, which is obtained by treatment with 7. The silicon alkoxide is one in which at least two alkoxy groups are bonded to a silicon atom, and the silicic acid blocked with a phosphoric acid or a phosphoric acid ester group according to any one of items 1, 2 and 6 above. Polymer. 8. The phosphoric acid or phosphorus according to any one of the above items 1, 2 and 6 to 7, wherein the condition for hydrolyzing the silicon alkoxide is to form a linear silicic acid polycondensate or a monocyclic silicic acid polycondensate. Silicic acid polymers blocked with acid ester groups. 9. The above-mentioned items 1, 2 and 6 wherein the first step of hydrolyzing the silicon alkoxide to form a silicic acid polycondensate uses about 0.5 to about 4 moles of organic solvent per silicon alkoxide. 10. A silicic acid polymer blocked with the phosphoric acid or phosphate ester group according to any one of to 8.

10. Item 1, 2 and 3 above, wherein the first step of hydrolyzing the silicon alkoxide to form a polycondensate of silicic acid uses from about 0.5 to about 2.5 moles of water per silicon alkoxide. A silicic acid polymer blocked with the phosphoric acid or phosphate ester group according to any one of 6 to 9. 11. The first step of hydrolyzing a silicon alkoxide to form a silicic acid polycondensate uses about 0.001 to about 0.5 moles of acid per silicon alkoxide. A silicic acid polymer blocked with the phosphoric acid or phosphate ester group according to any one of 6 to 10. 12. Phosphoric acid is selected from the group consisting of orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, chain polyphosphoric acid such as tetraphosphoric acid, trimetaphosphoric acid, cyclic polyphosphoric acid such as tetrametaphosphoric acid, and reticulated polyphosphoric acid. A silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group according to any one of Items 1, 2 and 6 to 11. 13. The phosphate or phosphate ester group according to any one of items 1, 2 and 6 to 12 above, wherein the phosphate ester is a mono-, di-, or tri-saturated or unsaturated hydrocarbon-substituted phosphate ester. Blocked silicic acid polymer. 14. Item 1, wherein the silicic acid polycondensation product formed by hydrolyzing a silicon alkoxide is subjected to a partial hydrolysis reaction in the presence of an acid.
A silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group according to any one of 2 and 6 to 13. 15. The silicon alkoxide is hydrolyzed to form a silicic acid polycondensate, and the resulting silicic acid polycondensate product is treated with phosphoric acid or a phosphoric acid ester to block with a phosphoric acid or a phosphoric acid ester group. Any one of the above items 1, 2 and 6 to 14 characterized in that the resulting silicic acid polymer is treated with a phosphoric acid or a phosphoric ester at least once after the product is partially hydrolyzed. 3. A silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group as described in 1 above.

16. A phosphoric acid or a phosphoric acid ester group blocked by a phosphoric acid or a phosphoric acid ester group according to any one of the above items 1, 2 and 6 to 15 for partially hydrolyzing a silicic acid polymer blocked with a phosphoric acid ester group. Silicic acid polymer. 17. The silicon alkoxide is hydrolyzed to form a silicic acid polycondensate, and the resulting silicic acid polycondensate product is treated with phosphoric acid or a phosphoric acid ester to block with a phosphoric acid or a phosphoric acid ester group. In the case of treating the product with a partial hydrolysis reaction,
The silicic acid polymer blocked with phosphoric acid or a phosphoric acid ester group according to any one of the above items 1, 2 and 6 to 16, which increases the degree of polymerization of the product by increasing the amount of acid used. .

18. Tetraethoxysilane in the presence of water, strong acid and lower alcohol at about 20-40 ° C for about 15-30
After the polycondensation reaction is carried out for a period of time, and the resulting silicic acid polycondensate is partially hydrolyzed under hydrolysis conditions, the partially hydrolyzed silicic acid polycondensate obtained is reacted with a tri-lower alkyl-substituted phosphate ester. The silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group according to the above item 1, which is characterized. 19. About 1.2 moles of tetraethoxysilane
-1.8 mol of water, about 0.005-0.02 mol of concentrated hydrochloric acid and about 0.5-2.0 mol of lower alcohol are allowed to undergo polycondensation reaction at about 0-40 ° C for about 1-30 hours. After partially hydrolyzing the obtained silicic acid polycondensate under hydrolysis conditions, about 1.0 mol (equivalent amount of Si contained) of the partially hydrolyzed silicic acid polycondensate obtained is added to about 0.1 to about 0.1 mol. The silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group according to the above item 1, wherein the silicic acid polymer is reacted with 3.0 mol of a tri-lower alkyl-substituted phosphoric acid ester. 20. An inorganic molded article produced by solidifying at least the phosphoric acid or phosphoric acid ester group-blocked silicic acid polymer according to any one of the above items 1 to 19 under hydrolysis conditions.

21. The silicon alkoxide is reacted under hydrolytic conditions to form a partial polycondensate of silicic acid, and the resulting product is treated at least once with phosphoric acid or a phosphoric ester to obtain a partial polycondensate. An inorganic adhesive characterized by being obtained by solidifying a silicic acid polymer blocked with an acid or a phosphate ester group under hydrolysis conditions. 22. 22. The inorganic adhesive according to item 21, wherein a silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group is hydrolyzed and solidified in the presence of an acid. 23. Tetraethoxysilane is subjected to polycondensation reaction in the presence of water, strong acid and lower alcohol at about 0 to 40 ° C. for about 1 to 30 hours, and the obtained silicic acid polycondensate is partially hydrolyzed under hydrolysis conditions, and then obtained. Partially hydrolyzed silicic acid polycondensate with tri-lower alkyl-substituted phosphate ester,
23. The inorganic adhesive as described in the above item 21 or 22, wherein the thus obtained phosphoric acid or phosphoric acid ester group-blocked silicic acid polymer is treated in the presence of an aqueous acid solution to be solidified.

24. About 1.0 mole tetraethoxysilane to about 1.2 to 1.8 mole water, about 0.005 to 0.0
Polycondensation reaction is carried out at about 0 to 40 ° C. for about 1 to 30 hours in the presence of 2 mol of concentrated hydrochloric acid and about 0.5 to 2.0 mol of lower alcohol, and the resulting silicic acid polycondensate is partially hydrolyzed. After the hydrolysis reaction, about 1.0 mol of the partially hydrolyzed silicic acid polycondensate (equivalent weight of Si contained) obtained is about 0.1-3.
The silicic acid polymer blocked with the phosphoric acid or the phosphoric acid ester group was reacted with 0 mol of a tri-lower alkyl-substituted phosphoric acid ester, and the silicic acid polymer blocked with the phosphoric acid or the phosphoric acid ester group was reacted with the polymer. Item 24. The product according to any one of Items 21 to 23 above, which is obtained by treating and solidifying at about 0 to 40 ° C in the presence of diluted hydrochloric acid in a weight ratio of about 0.1 to 0.6 with respect to the coalescence. Inorganic adhesive. 25. General formula

[0048]

[Chemical 9]

(In the formula, i is 1 to 20 and m is 0 to 20.
And R may be the same or different, and is a hydrogen atom or a carbon number 1
~ 6 alkyl group, -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 is a hydrogen atom,
An alkyl group having 1 to 6 carbon atoms, -PO (OR ¹ ) ₂ or-
An inorganic adhesive obtained by solidifying at least one of a phosphoric acid or a phosphoric acid ester group-blocked silicic acid polymer represented by Si (OR) ₃ . 26. The following formula

[0050]

[Chemical 10]

An inorganic adhesive characterized by being obtained by solidifying at least one selected from the group consisting of silicic acid polymers blocked with phosphoric acid or phosphoric acid ester groups represented by Agent. 27. At least one of the phosphoric acid or phosphoric acid ester group-blocked silicic acid polymers obtained by the production method according to any one of claims 1 to 21 is optionally mixed with an aggregate and an additive. A method for producing an inorganic molded body, which comprises solidifying without hydrolysis or blending under hydrolytic conditions. 28. 28. The method for producing an inorganic molded body according to item 27, wherein the silicic acid polymer blocked with a phosphoric acid or phosphoric acid ester group is hydrolyzed in the presence of an acid.

29. Tetraethoxysilane is subjected to polycondensation reaction in the presence of water, strong acid and lower alcohol at about 0 to 40 ° C. for about 1 to 30 hours, and the obtained silicic acid polycondensate is partially hydrolyzed under hydrolysis conditions, and then obtained. The partially hydrolyzed silicic acid polycondensate is reacted with a tri-lower alkyl-substituted phosphoric acid ester, and the obtained phosphoric acid or phosphoric acid ester group-blocked silicic acid polymer is treated in the presence of an aqueous acid solution to solidify. 29. The method for producing an inorganic molded body according to item 27 or 28 above. 30. About 1.2 moles of tetraethoxysilane
-1.8 mol of water, about 0.005-0.02 mol of concentrated hydrochloric acid and about 0.5-2.0 mol of lower alcohol are allowed to undergo polycondensation reaction at about 0-40 ° C for about 1-30 hours. After partially hydrolyzing the obtained silicic acid polycondensate under hydrolysis conditions, about 1.0 mol (containing Si equivalent) of the partially hydrolyzed silicic acid polycondensate obtained is about 0.1 to 3 0.0 mol of a tri-lower alkyl-substituted phosphoric acid ester, and the resulting phosphoric acid or a silicic acid polymer blocked with a phosphoric acid ester group is added in the presence of about 0.1 to 0.6 by weight of dilute hydrochloric acid. 0 to
30. The method for producing an inorganic molded body according to any one of the items 27 to 29, which is characterized by treating at 40 ° C. and solidifying.

31. The silicic acid polycondensation product formed by hydrolyzing tetraethoxysilane is
31. The method for producing an inorganic molded product according to item 29 or 30, which is a linear silicic acid polycondensate or a monocyclic silicic acid polycondensate. 32. General formula

[0054]

[Chemical 13]

(Where i is 1 to 20 and m is 0 to 20)
And R may be the same or different, and is a hydrogen atom or a carbon number 1
~ 6 alkyl group, -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 is a hydrogen atom,
An alkyl group having 1 to 6 carbon atoms, -PO (OR ¹ ) ₂ or-
Si (OR) ₃ ) at least one of which is solidified under a hydrolysis condition with or without optionally adding an aggregate and an additive as required. Method for manufacturing inorganic molded body. 33. The following formula

[0056]

[Chemical 14]

At least one selected from the group consisting of silicic acid esters represented by the formula (1) is characterized in that it is solidified under hydrolysis conditions with or without optional addition of aggregates and additives as required. And a method for producing an inorganic molded body. 34. An inorganic molded article obtained by the production method according to any one of items 27 to 33 above. 35. The silicon alkoxide is reacted under hydrolytic conditions to form a silicic acid partial polycondensate, and the resulting product is then treated at least once with phosphoric acid or a phosphoric acid ester to obtain the resulting polycondensate. An inorganic adhesive which is obtained by solidifying a silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group under a hydrolysis condition.

[0058]

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 A reaction for forming a silicic acid polymer was performed using tetraethoxysilane (special silicon reagent SP). (Oligomer synthesis reaction) 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 (special grade reagent) was distilled into this. 2.53 g (1.5 mol) of water was added, and further 100 mg (0.01 mol) of a 35% strength hydrochloric acid solution 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.

To analyze the properties of the oligomer in the oligomer-containing reaction mixture obtained in the above step (1), 15 g (1.5 mol) of trimethylsilyl chloride (TMSC, special grade reagent) was added to the product and stirred. While reacting. The low-boiling substances in the reaction mixture thus obtained are removed by evaporation, and a trimethylsilyl group (TMS) -blocked oligomer is obtained as a residue. The above example is referred to as Experimental Example 1. In the same manner, Experimental Examples 2 to 10 were performed by changing the amounts of distilled water, methanol and hydrochloric acid solution.
The amounts used are shown in Table 1.

[0060]

[Table 1]

GPC (Gel Permeation Chromatograph) was used to measure the molecular weight and molecular weight distribution of the obtained oligomer. Table 2 shows a summary of the results obtained in the above examples.

[0062]

[Table 2]

Example 2 (1) Oligomer synthesis reaction 200 g (10.0 mol) of tetraethoxysilane (TEOS) was placed in a round-bottomed flask containing a stir bar, and then 30.9 g of methanol and 25. 3 g (15.
0 mol) was added, and 1.0 g of 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 substance and the solvent in the oligomer-containing reaction mixture obtained in the above step are removed by evaporation to obtain polytetraethoxysilane (PTEOS) as a transparent and viscous liquid as a residue. The properties of the PTEOS 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.

[0065]

[Table 3]

(2) Blocking Reaction of Oligomer Distilled water and a catalytic amount of 1N hydrochloric acid were added to the oligomer-containing ethanol solution (using 99.5% ethanol) obtained in the above step (1), and the mixture thus obtained. Is allowed to react for 45 minutes with stirring at room temperature. To the partially hydrolyzed oligomer-containing reaction mixture thus obtained, triethyl phosphate (special grade reagent) was added,
The reaction is carried out at 80 ° C. for about 15 hours with stirring. The volatile low-boiling substances and the solvent in the blocked oligomer-containing reaction mixture obtained in the above step were removed by evaporation, and the residue was a colorless transparent viscous liquid, which was blocked with phosphoric acid groups. Ethoxysilane (PTEO
S) is obtained. Table 4 shows the blending ratio of the reagents used and the yield of the product.

[0067]

[Table 4]

The phosphate group blocked PTE obtained
IR and ¹ H NMR charts of the OS oligomer are shown in FIGS. 1 and 2. From the IR spectrum of FIG. 1, 3500
Since the Si—OH absorption intensity around cm ⁻¹ is weak, it can be confirmed that the blocking reaction is proceeding. Moreover, from the result of the ¹ H NMR chart in FIG.
It has been found that it is possible to introduce various proportions of phosphate groups into the oligomer.

Example 3 (1) Oligomer synthesis reaction Tetraethoxysilane (TEOS) was placed in an eggplant-shaped flask containing a stir bar, then methanol and distilled water were added thereto, and a 35% hydrochloric acid solution was further added. did. 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.

[0070]

[Table 5]

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

[0072]

[Table 6]

(2) Blocking Reaction of Oligomer Distilled water and a catalytic amount of 1N hydrochloric acid were added to the oligomer-containing ethanol solution (using 99.5% ethanol) obtained in the above step (1), and the mixture thus obtained. Is allowed to react for 45 minutes with stirring at room temperature. To the partially hydrolyzed oligomer-containing reaction mixture thus obtained, triethyl phosphate (special grade reagent) was added,
The reaction is carried out at 80 ° C. for about 3 hours with stirring. The volatile low-boiling substances and the solvent in the blocked 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.,
A colorless transparent viscous liquid is obtained as a residue, and polytetraethoxysilane (PTEOS) blocked with phosphoric acid groups is obtained. Table 7 shows the mixing ratio of the reagents used.

[0074]

[Table 7]

(3) Inorganic molded product forming reaction 1N hydrochloric acid was added to the PTEOS oligomer blocked with the phosphoric acid group obtained in the above step (2), and the mixture was stirred and mixed until it became transparent. The obtained liquid was treated with polypropylene (P.
P. ) And cast at room temperature to solidify. Table 8 shows the mixing ratios of the reagents used and the solidification reaction conditions.

[0076]

[Table 8]

Table 9 shows the physical properties of the obtained new PTEOS solidified product.

[0078]

[Table 9]

From the obtained results, it was found that when polytetraethoxysilane (PTEOS) oligomer having a relatively wide molecular weight distribution was used, the one having large compressive strength was obtained. Further, when a PTEOS oligomer having a large average molecular weight was used, one having a large compressive strength was obtained. The one having a relatively low degree of blocking by the phosphoric acid ester had a larger compressive strength.

From this, the mechanism as explained in FIG. 3 is expected. First, the silicic acid polymer represented by A is
As shown in (1), when it is usually cross-linked, it becomes a block, and even if each has strength, their bonds are almost only hydrogen bonds, so they become brittle. Also, strength against bending cannot be expected so much. However, in the case of linear molecules as shown by C, the linear molecules are entangled with each other, and the tensile strength is also increased. In addition, it becomes considerably strong against bending. When a flexible bond such as D is introduced between such linear molecules, toughness can be further developed. Examples of such flexible bond include hydrogen bond, ionic bond, and coordinate bond. It is also understood that the one basically has a linear structure.

In the case of the inorganic molded product of the present invention, it is considered that partial decomposition / bonding occurs in the presence of water as in E. In E, the bond that functions as a spring is considered to be a hydrogen bond between phosphate residues. Those capable of forming an ionic bond, a coordinate bond and the like include magnesium, calcium, manganese, aluminum such as Group II, Group III, Group VII and Group VIII of the periodic table of elements,
Titanium, zirconium, iron, cobalt, nickel,
Copper, zinc, cadmium, lead, chromium, molybdenum, tungsten, manganese, etc. may be mentioned. F represents the concept of the structure when a metal or the like is coordinated.

Example 4 (1) Oligomer Synthesis Reaction In a round-bottomed flask containing a stirrer, 1.0 mol of tetraethoxysilane (TEOS) and 1.0 mol of methanol were added.
And 1.4 mol of distilled water were added, and 0.01 mol of a 12 N hydrochloric acid solution was further added. The reaction mixture is reacted at room temperature (about 20 ° C.) for about 24 hours with stirring. The oligomer-containing reaction mixture obtained in the above step is concentrated to obtain a colorless transparent viscous liquid.

(2) Blocking Reaction of Oligomer The oligomer-containing solution obtained in the above step (1) was mixed with 9
2.0 mol of 9.5% ethanol, 1.0 mol of distilled water
And 1 drop of 1N hydrochloric acid are added, and the mixture thus obtained is reacted at room temperature (about 20 ° C.) for about 1 hour while stirring. To the partially hydrolyzed oligomer-containing reaction mixture thus obtained, 1.0 mol of triethyl phosphate ester (special grade reagent) is added and reacted at 80 ° C. for about 3 hours with stirring. The blocked oligomer-containing reaction mixture obtained in the above step is concentrated under reduced pressure to obtain a colorless transparent viscous liquid.

(3) Structural Analysis Instrumental analysis was performed using the above-obtained sample as an analysis sample. Mass spectrometry (GC-MS): Electron impact method (EI) and chemical ionization method (CI) were carried out under the instrumental analyzer and measurement conditions shown in Tables 10 and 11.

[0085]

[Table 10]

[0086]

[Table 11]

Nuclear Magnetic Resonance Spectroscopy (NMR): ³¹ P-NM
R and ²⁹ Si-NMR were carried out under the instrumental analyzer and measurement conditions shown in Tables 12 and 13.

[0088]

[Table 12]

[0089]

[Table 13]

The results of mass spectrometry (GC-MS) are shown in FIGS.
Shown in. From these data. Peak No. separated by gas chromatograph. Four
The compound of is ion peak 734 and fragment peak 5
97 was observed and this difference 137 was found to correspond to O = P (OEt) ₂ . ． Peak No. Also in the compound of No. 5, the difference between the ion peak of 748 in MS (CI) and the fragment peak 611 in MS (EI) is 137, which is also O = P.
It is recognized that it corresponds to (OEt) ₂ . ． Peak No. 1, No. 2 and No. In the compound of No. 3, no fragment corresponding to O = P (OEt) ₂ was observed, but -Et (28), -OEt (44), -H.
Fragments such as ₂ O (18) are present. No. 1-No. As the compound of 5, the identified structure is shown in FIG. Thus, this silicic acid polymer contains at least one or more [-Si-OP (OEt) ₂ =
It was found that the structure of [O] exists in the molecule.

The results of nuclear magnetic resonance spectroscopy (NMR) are shown in FIGS. From these. ^{From 31} P-NMR (FIGS. 9 and 10), it is observed that the chemical shift (−0.525 ppm) of the silicic acid polymer is different from that of triethyl phosphate (+0.067 ppm). This indicates that the phosphorus atom in the silicic acid polymer is in a different environment from the phosphorus atom of the starting material triethyl phosphate, and [-Si-OP (OE
t) ₂ = O] is present. ． ^{From 29} Si-NMR (FIGS. 11 and 12), when comparing before and after the treatment with triethyl phosphate, Q1 and Q2 were obtained.
It is observed that the chemical shifts of the are different. Further, there are Si peaks corresponding to Q3 and Q4. This indicates that the phosphorus atom is bonded to the oxygen on the silicon of Q1 and Q2 in the silicic acid polymer,
Furthermore, it shows that the silicon skeleton in the polymer has a branch. These observations support the above structure.

Example 5 (1) Oligomer Synthesis Reaction Tetraethoxysilane: distilled water: 35% hydrochloric acid solution: methanol at a molar ratio of 1 in an eggplant-shaped flask containing a stir bar.
(TEOS): 1.8 (H ₂ O): 0.0135% HC
1): 1.0 (Me-OH), and first, a solution of hydrochloric acid was added to a mixture of tetraethoxysilane, methanol and distilled water. The reaction mixture is reacted at room temperature (about 20 ° C.) for about 24 hours with stirring. The solvent and volatile substances are evaporated from the oligomer-containing reaction mixture obtained in the above step to obtain a P-TEOS oligomer.

(2) Blocking Reaction of Oligomer The oligomer-containing liquid obtained in the above step (1), 99.
First, 5% ethanol, distilled water and 1N hydrochloric acid were mixed at the compounding ratios shown in Table 14, the oligomer-containing liquid, ethanol and distilled water were mixed, and 1N hydrochloric acid was added in a catalytic amount. The mixture thus obtained is reacted at room temperature (about 20 ° C.) for about 45 minutes while stirring. Next, triethyl phosphate (special grade reagent) is added to the partially hydrolyzed oligomer-containing reaction mixture, and the mixture is reacted at 80 ° C. for about 3 hours with stirring. After the reaction was completed, the solvent and volatile substances were evaporated, and PT blocked with phosphoric acid was used.
An EOS oligomer is obtained.

[0093]

[Table 14]

(3) Inorganic molding formation reaction 1N hydrochloric acid was added to the phosphoric acid group-blocked P-TEOS oligomer obtained in the above step (2), and the mixture was stirred and mixed until it became transparent. The obtained liquid is poured into a mold (13 mmφ, H = 25 mm) made of polypropylene (PP) and solidified at room temperature. Table 15 shows the mixing ratios of the reagents used and the solidification reaction conditions.

[0095]

[Table 15]

(4) Physical Test A physical test was conducted on the molded product obtained in (3) above. In the physical test, the maximum strength and strain amount were measured for each age with a 5t universal testing machine. The size and weight of the specimen are measured, and the maximum strength, Young's modulus, strain rate, and specific strength are calculated. The measurement conditions of the autograph were the conditions shown in Table 16.

[0097]

[Table 16]

The test results are shown in FIGS. 13 and 14. From these results, the ratio of triethyl phosphate and silicic acid (P / S
It was found that the compressive strength and toughness can be controlled by changing the i ratio). Therefore, it can be expected that the use of the silicic acid polymer blocked with the phosphoric acid or phosphoric acid ester group of the present invention will result in better performance than the specific strength and toughness of ordinary concrete.

[0099]

According to the present invention, it is possible to control the hydrolysis and polycondensation reaction of silicon alkoxide, and partially inactivate the polycondensation reaction point during the production of the inorganic silicic acid polymer, It provides a way to control its structure at the molecular level. According to the present invention, a more linear inorganic silicic acid polymer can be synthesized more uniformly, so that an inorganic material having a flexible structure can be obtained. In addition, in the synthetic reactions that have been performed so far by adjusting the catalyst or pH, not only the reproducibility of the reaction is poor, but also the obtained product has a wide molecular weight distribution range and is not uniform. However, according to the present invention, it is possible to synthesize an inorganic silicic acid polymer which is reproducible and uniform and which is more linear.

According to the present invention, a method for obtaining a uniform and highly pure or highly functional inorganic silicic acid polymer by an inexpensive and simple production method is opened. The product obtained according to the present invention is of uniform and high quality, rich in flexibility, excellent in heat resistance and combustion resistance, and also has radiation resistance, and its hardness is high and abrasion resistance is high. is there. Since the inorganic silicic acid polymer of the present invention can be produced by a simple and simple operation, it is of high quality and inexpensive, and can be a uniform product.
It is also possible to easily impart oil resistance and solvent resistance. The inorganic silicic acid polymer of the present invention makes use of its characteristics so as to have a heat resistant material, a non-combustible material, a heat ray reflective material, an electric insulating material, a transparent conductive material, an anticorrosive material, a chemical resistance imparting material, and an abrasion resistance. It is expected to be used as a special surface protection material and a special functional material having antireflection and lubricating effects. 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 shows the IR spectrum of a phosphate group blocked PTEOS oligomer obtained by treatment according to the invention.

FIG. 2 shows a ¹ H NMR chart of a phosphate group blocked PTEOS oligomer obtained by the treatment according to the present invention.

FIG. 3 shows a mechanism for expressing properties such as strength of the inorganic molded body according to the present invention.

FIG. 4 shows the results of mass spectrometry (GC-MS) of a silicic acid polymer blocked with phosphate groups obtained by the treatment according to the present invention.

FIG. 5 shows the results of mass spectrometry (GC-MS) of a phosphoric acid group blocked silicic acid polymer obtained by the treatment according to the present invention.

FIG. 6 shows the results of mass spectrometry (GC-MS) of a phosphoric acid group blocked silicic acid polymer obtained by the treatment according to the present invention.

FIG. 7 shows the results of mass spectrometry (GC-MS) of a phosphoric acid group blocked silicic acid polymer obtained by the treatment according to the present invention.

FIG. 8 shows the identified structure of a silicic acid polymer blocked with phosphate groups obtained by treatment according to the invention.

FIG. 9: Nuclear magnetic resonance spectroscopy analysis of phosphoric acid group blocked silicic acid polymers obtained by treatment according to the invention (NM
The spectrum of R) is shown.

FIG. 10: Nuclear magnetic resonance spectroscopy analysis of phosphoric acid group blocked silicic acid polymers obtained by treatment according to the invention (NM
The spectrum of R) is shown.

FIG. 11: Nuclear magnetic resonance spectroscopy (NM) of phosphate group blocked silicic acid polymers obtained by treatment according to the invention.
The spectrum of R) is shown.

FIG. 12: Nuclear magnetic resonance spectroscopy (NM) of a phosphate group blocked silicic acid polymer obtained by treatment according to the present invention.
The spectrum of R) is shown.

FIG. 13 shows the relationship between the compressive strength and the phosphate / silicon ratio of the inorganic molded body obtained according to the present invention.

FIG. 14 shows the relationship between the Young's modulus and the phosphate / silicon ratio of the inorganic molded body obtained according to the present invention.

[Chemical 11]

[Chemical 12]

[Table 17]

[Table 18]

Claims (25)

[Claims] 1. A method comprising subjecting a silicon alkoxide to a hydrolysis reaction to form a silicic acid polycondensate, and then treating the resulting silicic acid polycondensate product at least once with phosphoric acid or a phosphoric acid ester. And a method for producing a silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group. 2. A silicon alkoxide is hydrolyzed under polycondensation conditions to form a silicic acid polycondensate, and the resulting silicic acid polycondensate product is treated with phosphorus at least once after the partial hydrolysis reaction treatment. The method for producing a silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group according to claim 1, wherein the method is a treatment with an acid or a phosphoric acid ester. 3. A silicic acid polycondensate product formed by hydrolyzing a silicon alkoxide is a linear silicic acid polycondensate or a monocyclic silicic acid polycondensate.
Or the method for producing a silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group according to 2 above. 4. The silicic acid polycondensation product formed by hydrolyzing a silicon alkoxide has a number average molecular weight range of 1000 or more and a weight average molecular weight / number average molecular weight ratio range of 1.2. The method for producing a silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group according to any one of claims 1 to 3, which is the above oligomer. 5. The silicon alkoxide has at least two alkoxide groups bonded to a silicon atom and is blocked with a phosphoric acid or a phosphoric acid ester group according to any one of claims 1 to 4. Method for producing silicic acid polymer. 6. The phosphoric acid according to any one of claims 1 to 5, wherein the condition for hydrolyzing the silicon alkoxide is to form a linear silicic acid polycondensate or a monocyclic silicic acid polycondensate. A method for producing a silicic acid polymer blocked with a phosphate group. 7. The method of hydrolyzing a silicon alkoxide to form a silicic acid polycondensate, wherein the first step uses about 0.5 to about 4 moles of organic solvent per silicon alkoxide. 7. The method for producing a silicic acid polymer blocked with a phosphoric acid or phosphoric acid ester group according to any one of items 1 to 6. 8. The method of hydrolyzing a silicon alkoxide to form a silicic acid polycondensate, wherein the first step uses about 0.5 to about 2.5 moles of water per silicon alkoxide. A method for producing a silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group according to any one of 1 to 7. 9. The method of hydrolyzing a silicon alkoxide to form a polycondensate of silicic acid, wherein the first step uses about 0.001 to about 0.5 moles of acid per silicon alkoxide. 9. A method for producing a silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group according to any one of 1 to 8. 10. A chain polyphosphoric acid such as orthophosphoric acid, pyrophosphoric acid, triphosphoric acid or tetraphosphoric acid,
A silicic acid blocked with a phosphoric acid or a phosphoric acid ester group according to any one of claims 1 to 9, which is selected from the group consisting of cyclic polyphosphoric acid such as trimetaphosphoric acid and tetrametaphosphoric acid, and network polyphosphoric acid. A method for producing an acid polymer. 11. The phosphoric acid or phosphoric acid ester group according to claim 1, wherein the phosphoric acid ester is a mono-, di-, or tri-saturated or unsaturated hydrocarbon-substituted phosphoric acid ester. Of producing a silicic acid polymer blocked with a silane. 12. The silicic acid polycondensation product, which is formed by hydrolyzing a silicon alkoxide, is partially hydrolyzed in the presence of an acid, according to any one of claims 1 to 11. A method for producing a silicic acid polymer blocked with the phosphoric acid or phosphoric acid ester group according to the description. 13. A silicic acid polycondensate is formed by subjecting a silicon alkoxide to a hydrolysis reaction, and the resulting silicic acid polycondensate product is treated with phosphoric acid or a phosphoric acid ester to obtain phosphoric acid or phosphoric acid. 13. A silicic acid polymer blocked with an acid ester group, which is then subjected to a partial hydrolysis reaction treatment and further treated at least once with phosphoric acid or a phosphoric acid ester. 5. A method for producing a silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group according to any one of the above. 14. The phosphoric acid or phosphoric acid ester group according to claim 1, wherein the silicic acid polycondensate blocked with a phosphoric acid or phosphoric acid ester group is partially hydrolyzed in the presence of an acid. Process for producing blocked silicic acid polymer. 15. Tetraethoxysilane is subjected to polycondensation reaction in the presence of water, a strong acid and a lower alcohol at about 0 to 40 ° C. for about 1 to 30 hours, and the obtained silicic acid polycondensate is partially hydrolyzed under hydrolysis conditions. After the reaction, the resulting partially hydrolyzed silicic acid polycondensate is reacted with a tri (lower alkyl) -substituted phosphoric acid ester, and the silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group according to claim 1. Manufacturing method of coalescence. 16. About 1.0 mole tetraethoxysilane to about 1.2 to 1.8 mole water, about 0.005 to 0.02.
Polycondensation reaction is performed at about 0 to 40 ° C. for about 1 to 30 hours in the presence of concentrated concentrated hydrochloric acid and about 0.52 to 2.0 mol of lower alcohol, and the obtained silicic acid polycondensate is partially hydrolyzed. After the hydrolysis reaction, about 1.0 mol (containing equivalent amount) of the partially hydrolyzed silicic acid polycondensate obtained is reacted with about 0.1 to 3.0 mol of a tri-lower alkyl-substituted phosphate ester. The method for producing a silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group according to claim 1. 17. The silicic acid polycondensate product formed by hydrolyzing tetraethoxysilane is a linear silicic acid polycondensate or a monocyclic silicic acid polycondensate, according to claim 15 or 16. A method for producing a silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group. 18. A silicic acid polymer blocked with a phosphoric acid or phosphoric acid ester group has the general formula: (In the formula, i is 1 to 20, m is 0 to 20, R may be the same or different, and a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, -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 may be a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, —PO (OR ¹ ) ₂ or —Si (OR) ₃
The method for producing a silicic acid polymer blocked with phosphoric acid or a phosphoric acid ester group according to claim 1, wherein the silicic acid ester is represented by 19. A silicic acid polymer blocked with a phosphoric acid or phosphoric acid ester group is represented by the following formula: The method for producing a silicic acid polymer blocked with phosphoric acid or a phosphoric acid ester group according to claim 1 or 18, which is selected from the group consisting of silicic acid esters represented by: 20. A silicic acid polycondensate is formed by subjecting a silicon alkoxide to a hydrolysis reaction, and the resulting silicic acid polycondensate product is treated at least once with phosphoric acid or a phosphoric acid ester. A phosphoric acid or a phosphoric acid ester group, which is blocked with a phosphoric acid or a phosphoric acid ester group, is solidified under hydrolysis conditions to produce an inorganic molded silicic acid polymer. Of producing the obtained silicic acid polymer. 21. An inorganic molded article obtained by solidifying a silicic acid polymer blocked with a phosphoric acid or a phosphate ester group obtained by the production method according to any one of claims 2 to 19 under a hydrolysis condition. The method for producing a silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group according to claim 20, wherein the silicic acid silicic acid polymer is produced. 22. A silicic acid polymer blocked with a phosphoric acid or phosphoric acid ester group is hydrolyzed in the presence of an acid to produce an inorganic molded silicic acid polymer. A method for producing a silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group. 23. Tetraethoxysilane is subjected to a polycondensation reaction in the presence of water, a strong acid and a lower alcohol at about 0 to 40 ° C. for about 1 to 30 hours, and the obtained silicic acid polycondensate is partially hydrolyzed under hydrolysis conditions. After the reaction, the resulting partially hydrolyzed silicic acid polycondensate is reacted with a tri-lower alkyl-substituted phosphoric acid ester, and the obtained phosphoric acid or a phosphoric acid ester group-blocked silicic acid polymer is added in the presence of an aqueous acid solution. The silicic acid polymer blocked with phosphoric acid or a phosphoric acid ester group according to any one of claims 20 to 22, wherein the silicic acid polycondensate formed into an inorganic molded body is treated with the above-mentioned compound and solidified. Manufacturing method. 24. About 1.0 mole of tetraethoxysilane, about 1.2 to 1.8 moles of water, about 0.005 to 0.02.
Polycondensation reaction is performed at about 0 to 40 ° C. for about 1 to 30 hours in the presence of concentrated concentrated hydrochloric acid and about 0.5 to 2.0 mol of lower alcohol, and the obtained silicic acid polycondensate is partially hydrolyzed. After the hydrolysis reaction, about 1.0 mol of the obtained partially hydrolyzed silicic acid polycondensate (equivalent amount of Si contained) is added to about 0.1.
The silicic acid polymer blocked with phosphoric acid or a phosphoric acid ester group was reacted with 3.0 mol of a tri-lower-alkyl-substituted phosphoric acid ester, and in the presence of dilute hydrochloric acid at a weight ratio of about 0.1 to 0.6. 24. Blocking with phosphoric acid or phosphate ester groups according to any one of claims 20 to 23, characterized in that it is treated at about 0 to 40 [deg.] C. and solidified to produce an inorganic molded silicic acid polymer. Method for producing silicic acid polymer. 25. The silicic acid polycondensate product formed by hydrolyzing tetraethoxysilane is a linear silicic acid polycondensate or a monocyclic silicic acid polycondensate, according to claim 23 or 24. A method for producing a silicic acid polymer blocked with a phosphoric acid or a phosphoric acid ester group according to any one of claims.