JPH11209472A - Preparation of sulfonic group-containing organic macromolecular siloxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an organic macromolecular siloxane containing a sulfonic group having a widened applicable range with improved water resistance by hydrolysis and dehydration condensation of a mixture of raw materials comprising as ingredients an alkoxy silane containing a sulfonic group and another alkoxysilane capable of forming an organic macromolecular siloxane. SOLUTION: A mixture of raw materials comprising at least one alkoxy silane compound containing a sulfonic group which can form a macromolecular siloxane matrix and is represented by the formula: R<a> n SiX4-n (n is an integer of 1-3; R<a> is a 1-15C hydrocarbyl group having at least one sulfonic group; X is at least one selected from the group consisting of alkoxy groups; and Si is a silicon atom) and at least one alkoxy silane compound which can form a macromolecular siloxane matrix and is represented by the formula: R<b> n SiX4-n (n is an integer of 0-3; Rb is a 1-20C hydrocarbyl group; X is at least one selected from the group consisting of alkoxy groups; and Si is a silicon atom) is subjected to hydrolysis and dehydration condensation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for synthesizing a high water-resistant sulfonic acid group-containing organic high molecular siloxane useful as an ion exchanger and a solid acid catalyst.

[0002]

2. Description of the Related Art A strongly acidic ion exchanger having a sulfonic acid group is used, for example, as a solid acid catalyst in desalination of water and an aqueous solution, and chemical synthesis. Cation exchangers used in most cases have a polystyrene backbone,
It is generally called a cation exchange resin containing phenylsulfonic acid groups. Cation exchange resins have low heat resistance, and the upper limit of use is generally 100 to 130 ° C. In addition, it has disadvantages such as breakage due to remarkable expansibility and brittleness of mechanical strength.

On the other hand, an organic polymer siloxane is an example of an inorganic polymer ion exchanger. Organic polymer siloxanes are described in JP-A-59-20325, JP-A-61-272237, and JP-A-8-2085.
No. 39 discloses a sulfonic acid group-containing organic high molecular siloxane in which a sulfonic acid group is bonded to a matrix by an organic spacer group. It is disclosed that the sulfonic acid group-containing organic high molecular siloxane can be obtained by an oxidation treatment of a polysulfide polymer and a sulfonation treatment of a solid organic high molecular siloxane.

Japanese Patent Application Laid-Open No. Hei 6-207012 discloses a method in which an aqueous solution of a siloxane having a sulfonic acid group is incorporated during hydrolysis and dehydration condensation with another alkoxysilane to fix the sulfonic acid group in a polymer siloxane matrix. It has been disclosed. Since these sulfonic acid group-containing organic high molecular siloxanes have high heat resistance and high mechanical strength, those having high water resistance are expected to be applied to desalting and acid-catalyzed reactions under severe conditions.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to expand the range of application of a sulfonic acid group-containing organic high molecular siloxane by improving the water resistance of the compound.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to increase the water resistance of a sulfonic acid group-containing organic high molecular siloxane. The water resistance of the sulfonic acid group-containing organic high molecular siloxane synthesized by hydrolysis and dehydration-condensation of a raw material mixture containing alkoxysilane and another alkoxysilane capable of forming an organic high molecular siloxane as a component is remarkably improved. They have found and completed the present invention.

Namely, the present invention provides [Claim 1] _{R a n SiX (4- n)} ( wherein n capable of forming a polymeric siloxane matrix is 1 to 3 integers, R _a is at least 1 X is a hydrocarbon group having 1 to 15 carbon atoms having the above sulfonic acid group, and X is at least one selected from the group consisting of alkoxy groups;
Si represents a silicon atom. At least one alkoxysilane compound having a sulfonic acid group represented by), R _{b n} SiX capable of forming a polymeric siloxane matrix
_(4-n) (wherein n is an integer of 0 or more and 3 or less, R _b is a hydrocarbon group having 1 or more and 20 or less, and X is at least one selected from the group consisting of alkoxy groups. Yes, Si
Represents a silicon atom. A method for producing a sulfonic acid group-containing organic high molecular siloxane, comprising hydrolyzing and dehydrating at least one of the alkoxysilane compounds represented by the formula [2]. [Claim 2] R capable of forming a high molecular siloxane matrix _{a n SiX (4- n) (} n in the formula is 1 to 3 integers, R _a is a hydrocarbon group having 1 to 15 carbon atoms and having at least 1 or more sulfonic acid groups, X is an alkoxy At least one selected from the group consisting of
Si represents a silicon atom. At least one alkoxysilane compound having a sulfonic acid group represented by), R _{b n} SiX capable of forming a polymeric siloxane matrix
_(4-n) (wherein n is an integer of 0 or more and 3 or less, R _b is a hydrocarbon group having 1 or more and 20 or less, and X is at least one selected from the group consisting of alkoxy groups. Yes, Si
Represents a silicon atom. 2. The method according to claim 1, wherein the raw material mixture containing at least one of the alkoxysilane compounds represented by the formula) is hydrolyzed and dehydrated and condensed. 3. The sulfonic acid group is an aromatic sulfonic acid group. (4) The method according to (3), wherein the aromatic sulfonic acid group is a phenylsulfonic acid group, or (5) the alkoxy group is a methoxy group. , An ethoxy group, an n-propoxy group, or an isopropoxy group, the method according to any one of claims 1 to 4, [6] a method according to any one of claims 1 to 5, Sulfonic acid group-containing organic high molecular siloxane.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The sulfonic acid group-containing alkoxysilane compound capable of forming the polymer siloxane matrix used in the present invention is a compound in which a hydrocarbon group having a sulfonic acid group is directly bonded to a silicon atom, and is a mixture of an alkoxysilane compound such as ethyl silicate. And an alkoxysilane compound which can be solidified by a usual sol-gel reaction to form a gel-like substance.

[0009] Specific examples of the sulfonic acid group-containing alkoxysilane compound capable of forming a polymeric siloxane _{matrix, R a n SiX (4-} n) ( wherein n is 1 to 3 an integer, R _a is a hydrocarbon group having at least one sulfonic acid group and having 1 to 15 carbon atoms, and X is
Is at least one selected from the group consisting of alkoxy groups, and Si represents a silicon atom. )). The sulfonic acid group includes an alkylsulfonic acid group and an aromatic sulfonic acid group. Examples of the aromatic sulfonic acid group include a phenylsulfonic acid group.

In the present invention, at least one selected from sulfonic acid group-containing alkoxysilane compounds capable of forming a polymer siloxane matrix obtained by the above-described method and R capable of forming a polymer siloxane matrix.
_{b n} SiX _(4-n) (where n is an integer of 0 to 3;
R _b is a hydrocarbon group having 1 to 20 carbon atoms, X is at least one selected from the group consisting of alkoxy groups, and Si represents a silicon atom. ), The gelation of the mixed sol obtained by hydrolyzing at least one of the alkoxysilane compounds represented by
An organic high molecular siloxane having a sulfonic acid group forming a silica matrix can be produced.

X in each of the above general formulas represents at least one selected from the group consisting of an alkoxy group, and the silicon-X bond is decomposed by hydrolysis,
It is a group that makes it possible to form a polymeric siloxane bond. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy and other alkylalkoxy groups, phenoxy groups, and naphthoxy groups and other aromatic compounds. Group alkoxy group and the like. The present invention is not limited only to these alkoxy groups, and may be a mixture of these substituents.

[0012] R _{a n} The amount of SiX _(4-n) and _{R b n SiX (4-n} ), R a n SiX (4-n) relative to 1 mol, usually R _{b n} SiX _{(4 -n)} is used in an amount of 0.5 to 100 mol, preferably 1 to 50 mol.

Here, the mixed gelation in the present invention will be described. The mixed gelation in the present invention is sufficiently achieved by a general mixed sol-gel reaction of different alkoxysilanes. As a specific example of a mixed gelation method that is easy to carry out, an alkoxysilane compound having an organic sulfonic acid group as an acid component of a catalyst is charged in a desired amount, and R _{b n} is added to obtain water resistance. SiX _(4-n) (where n is an integer of 0 or more and 3 or less, and R _b has 1 or more carbon atoms and 2 or less.
A hydrocarbon group of 0 or less, X is at least one selected from the group consisting of alkoxy groups, and Si represents a silicon atom. ) Is mixed with at least one of the alkoxysilane compounds represented by the formula (1), and if necessary, a uniform mixed solution is prepared using a solvent such as ethanol. After adding an amount of water necessary for hydrolysis of the alkoxy group thereto, the mixture is usually stirred at a temperature of 10 to 200 ° C, preferably 30 to 1 ° C.
The reaction is carried out at 00 ° C. for 1 hour to 3 weeks under acidic conditions.
The obtained high viscosity liquid is generally called silica sol.

To the above-mentioned sol, an excess of water and aqueous ammonia are added to the amount of water required for hydrolysis of the alkoxy group.
Preferably, the gel is formed at 30 to 100 ° C. for 1 hour to 3 weeks. At this time, if necessary, the mixture may be heated and stirred to ripen it for a long time. In carrying out the gelation, the gelation may be carried out by diluting in a medium such as an alcohol or an aliphatic saturated hydrocarbon (hexane, heptane, etc.) which is inert to the sol.

The obtained gel can be isolated by filtration or by distilling off the solvent. Since the sulfonic acid in this gel is of the ammonium salt type or the like, it must be returned to the acid form by acid treatment with hydrochloric acid or the like in order to use it as an ion exchanger or a solid acid catalyst. In the present invention, the amount of sulfonic acid at the time of preparation is not particularly limited, but is preferably 0.05 to 3, preferably 0.3 to 2 in terms of milligram equivalent (meq / g: cation exchange amount per gram).
It is recommended that milligram equivalents be used. Of course, the present invention is not limited to only these ranges.

[0016]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples. (A) Production of sulfonic acid group-containing ethoxysilane in ethanol solution 200 ml of methylene chloride and 124.02 g (0.585 mol) of trichlorophenylsilane were placed in a two-necked 500 ml round bottom flask equipped with a dropping funnel, and cooled with ice. . 46.80 g of liquid SO ₃ (0.585 m
ol) in 100 ml of methylene chloride
It was added dropwise over 0 minutes. Thereafter, the ice bath was removed, and the mixture was stirred at room temperature for 5 hours. The dropping funnel was removed, and the mixture was heated at 100 ° C. for 1 hour under normal pressure using an oil bath to distill off methylene chloride and unreacted SO ₃ . After cooling, dry ethanol 16 at room temperature
1.50 g was added dropwise over 30 minutes, and the mixture was refluxed for 50 hours while bubbling nitrogen, and reacted while removing generated hydrogen chloride. 238.60 g of an ethanol solution of phenylsulfonic acid group-containing ethoxysilane containing unreacted phenylethoxysilane was used as an ethanol solution of sulfonic acid group-containing ethoxysilane in preparing a sulfonic acid group-containing organic high molecular siloxane.

Example 1 In a two-necked 500 ml round bottom flask equipped with a stirring bar, 26.00 g of the above-mentioned sulfonic acid group-containing ethoxysilane ethanol solution and 83.2 g of tetraethoxysilane (0.2 g) were added.
(40 mol) 100 ml of ethanol was added and mixed.
To this, 10.14 g (0.56 mol) of water was added dropwise over 30 minutes. It was then heated and stirred at 80 ° C. for 48 hours. Further, 5.07 g (0.28 mol) of water was added and 1
Stirring for 0 h increased the viscosity of the solution. This was allowed to cool, a mixture of 30 ml of 28% aqueous ammonia and 150 ml of water was added dropwise, and stirred at room temperature for 4 hours.
Stirred for days. This was separated by filtration to obtain a white solid. After the obtained solid was washed with 1000 ml of pure water, 300 ml of 3N hydrochloric acid was added, and the mixture was stirred at room temperature for 1 hour to return to a proton type. After washing well with a large amount of pure water, 100 ° C under reduced pressure
For 4 hours to obtain 30.00 g of an organic polymer siloxane having a sulfonic acid group (referred to as siloxane 1). The cation exchange capacity of the present sulfonic acid group-containing organic high molecular siloxane was 1.02 meq / g.
In a 1000 ml round bottom flask equipped with a reflux condenser equipped with a stirring rod, 20.0 g of the above siloxane 1 and 500 pure water were added.
Then, the mixture was heated and stirred at 85 ° C. for 15 hours. The suspension was filtered while hot and washed with a large amount of pure water. The obtained solid was dried under reduced pressure at 100 ° C. for 4 hours, and the amount of cation exchange was measured. The above treatment was repeated, and the amount of cation exchange was measured each time. The results are shown in Table 1.

EXAMPLE 2 26.00 g of the above-mentioned sulfonic acid group-containing ethoxysilane ethanol solution and 60.8 g of tetramethoxysilane (0.
(40 mol) 100 ml of ethanol was added and mixed.
To this, 10.14 g (0.56 mol) of water was added dropwise over 30 minutes. It was then heated and stirred at 80 ° C. for 48 hours. Further, 5.07 g (0.28 mol) of water was added and 1
Stirring for 0 h increased the viscosity of the solution. The mixture was allowed to cool, a mixture of 30% 28% aqueous ammonia and 150 ml of water was added dropwise, and the mixture was stirred at room temperature for 4 hours and then at 65 ° C for 6 days. This was separated by filtration to obtain a white solid. After the obtained solid was washed with 1000 ml of pure water, 300 ml of 3N hydrochloric acid was added, and the mixture was stirred at room temperature for 1 hour to return to a proton type. After washing well with a large amount of pure water,
After drying at 4 ° C. for 4 hours, 30.00 g of an organic polymer siloxane having a sulfonic acid group (referred to as siloxane 2) was obtained. The cation exchange capacity of the present sulfonic acid group-containing organic high molecular siloxane was 1.00 meq / g.
In a 1000 ml round bottom flask equipped with a reflux condenser equipped with a stirring rod, 20.0 g of the siloxane 2 and 500 pure water were added.
Then, the mixture was heated and stirred at 85 ° C. for 15 hours. The suspension was filtered while hot and washed with a large amount of pure water. The obtained solid was dried under reduced pressure at 100 ° C. for 4 hours, and the amount of cation exchange was measured. The above treatment was repeated, and the amount of cation exchange was measured each time. The results are shown in Table 1.

Example 3 In a two-necked 500 ml round bottom flask equipped with a stirring rod, 26.00 g of the above sulfonic acid group-containing ethoxysilane ethanol solution and 105.6 g of tetrapropoxysilane were added.
(0.40 mol) 100 ml of ethanol was added and mixed. To this, add 10.14 g (0.56 mol) of water to 30
Dropped over minutes. It is then heated and heated at 80 ° C. for 48 hours.
Stirred for hours. Further, when 5.07 g (0.28 mol) of water was added and stirred for 10 hours, the viscosity of the solution increased. This was allowed to cool, a mixture of 30 ml of 28% aqueous ammonia and 150 ml of water was added dropwise, and the mixture was stirred at room temperature for 4 hours.
Stirred at C for 6 days. This was separated by filtration to obtain a white solid. After washing the obtained solid with 1000 ml of pure water, 3
300 ml of N hydrochloric acid was added, and the mixture was stirred at room temperature for 1 hour to return to a proton form. After being thoroughly washed with a large amount of pure water, it is dried under reduced pressure at 100 ° C. for 4 hours, and organic polymer siloxane having a sulfonic acid group (referred to as siloxane 3) 30.00.
g was obtained. The cation exchange capacity of the present sulfonic acid group-containing organic high molecular siloxane was measured to be 0.99 meq / g. 1000 m with reflux condenser fitted with stir bar
20.0 g of the above-mentioned siloxane 3 and 500 ml of pure water were put into a round bottom flask and heated and stirred at 85 ° C. for 15 hours. The suspension was filtered while hot and washed with a large amount of pure water. The obtained solid was dried under reduced pressure at 100 ° C. for 4 hours, and the amount of cation exchange was measured. The above treatment was repeated, and the amount of cation exchange was measured each time. The results are shown in Table 1.

COMPARATIVE EXAMPLE 1 10 g of a phenyl group-containing SiO ₂ crosslinked organic high molecular siloxane composed of C ₆ H ₅ Si _1.5 · SiO ₂ units was
It was suspended in 0 ml. This was stirred at 80 ° C. for 3 hours, allowed to cool, added with a large amount of pure water, and filtered. The obtained solid was washed with pure water and dried under reduced pressure at 100 ° C. for 4 hours. Thus, 8 g of an organic high molecular siloxane (referred to as siloxane 4) having a sulfonic acid group obtained by sulfonating the solid was obtained. The cation exchange capacity of the present sulfonic acid group-containing organic high molecular siloxane was measured to be 0.99 meq / g. 20.0 g of the siloxane 4 and 500 ml of pure water were put into a 1000 ml round bottom flask equipped with a reflux condenser equipped with a stirring rod,
The mixture was heated and stirred for 5 hours. The suspension was filtered while hot and washed with a large amount of pure water. The obtained solid was dried under reduced pressure at 100 ° C. for 4 hours, and the amount of cation exchange was measured. The above treatment was repeated, and the amount of cation exchange was measured each time. The results are shown in Table 1.

Comparative Example 2 A sulfonic acid group-containing organic polymer siloxane was prepared by sulfonating a solid organic polymer siloxane according to Example 3 of JP-A-59-20325. S ₂ (C
H ₂ CH ₂ CH ₂ Si _1.5 ) ₂ · SiO ₂ (S content 0.26 m
ol) of 30 g of a disulfide group-containing SiO ₂ crosslinked organic high molecular siloxane was suspended in 100 ml of water. Cool the temperature to 5 ° C and add 40% hydrogen peroxide solution 4
0.4 g was added, and the mixture was stirred at 5 ° C for 1 hour. This is 100
ml of water was added and the solid was filtered off. It was washed with 500 ml of pure water and dried at 120 ° C. for 6 hours. Further at 250 ° C 4
After heat treatment for 8 hours, this was treated with Soxhlet for 6 hours, and then dried at 100 ° C. under reduced pressure for 4 hours. Organic polymer siloxane having sulfonic acid group (referred to as siloxane 5)
30 g were obtained. 1.01 meq / g as a result of measuring the cation exchange capacity of the present sulfonic acid group-containing organic high molecular siloxane
Met. 100 with reflux condenser fitted with stir bar
20.0 g of the above siloxane 5 in a 0 ml round bottom flask,
500 ml of pure water was added, and the mixture was heated and stirred at 85 ° C. for 15 hours. The suspension was filtered while hot and washed with a large amount of pure water.
The obtained solid was dried under reduced pressure at 100 ° C. for 4 hours, and the amount of cation exchange was measured. The above treatment was repeated, and the amount of cation exchange was measured each time. The results are shown in Table 1.

Comparative Example 3 A sulfonic acid group-containing siloxane aqueous solution was prepared according to Example 1 of JP-A-5-271243, and was used to prepare a solid sulfonic acid group-containing organic compound according to Example 1 of JP-A-6-207022. Preparation of molecular siloxane was performed. In a two-necked 10 l round bottom flask equipped with a stirring rod, S ₂ (C
_{H 2 CH 2 CH 2 Si (} OC 2 H 5) 3) Put ₂ 1500 g, was added ethanol 1500 ml. While this was heated to 50 ° C., 600 g of a 0.1 N hydrochloric acid aqueous solution was added dropwise over 30 minutes. Further, 2000 ml of water was added and the mixture was refluxed for 2 hours. After cooling, the mixture was filtered and the white solid was washed four times with 2000 ml of water. The white solid was suspended in 1700 ml of water and 3
800 g of 5% aqueous hydrogen peroxide was added. This is 40-50
Stir at 3 ° C. for 3 hours and then add another 35% aqueous hydrogen peroxide 8
00 g was added. This was stirred at 60 ° C. for 4 hours and then at 100 ° C. for 4 hours. The almost transparent aqueous solution was filtered, and the obtained aqueous solution was used as a sulfonic acid group-containing organic polymer siloxane aqueous solution as a raw material for preparing the following sulfonic acid group-containing organic polymer siloxane. 250 ml of the above sulfonic acid group-containing organic polymer siloxane aqueous solution was placed in a two-necked 3000 ml round bottom flask equipped with a stirring rod,
To this, 421.9 g of tetraethoxysilane (2.03 m
ol) was added dropwise at a temperature of 40 ° C. over 5 minutes. Then stirring at room temperature for 45 minutes increased the viscosity of the solution. To this, 1300 ml of industrial xylene was added. 40 in a two-layer system
Stirred at C for 1 h, heated to reflux for 1.5 h. After standing to cool, the mixture was filtered off, and 500 ml of 1N hydrochloric acid was added to the obtained solid, followed by stirring at 150 ° C. for 48 hours in an enamel-coated autoclave. Thereafter, the mixture was cooled, filtered, and sufficiently washed with pure water. This was dried at 100 ° C. under reduced pressure for 4 hours to obtain 162.00 g of a sulfonic acid group-containing organic high molecular siloxane (referred to as siloxane 6). The cation exchange capacity of the present sulfonic acid group-containing organic high molecular siloxane was determined to be 1.03 meq / g. 20.0 g of the above siloxane 6 and 500 ml of pure water were placed in a 1000 ml round bottom flask equipped with a reflux condenser equipped with a stirring rod, and heated at 85 ° C.
The mixture was heated and stirred for 5 hours. The suspension was filtered while hot and washed with a large amount of pure water. The obtained solid was dried under reduced pressure at 100 ° C. for 4 hours, and the amount of cation exchange was measured. The above treatment was repeated, and the amount of cation exchange was measured each time. The results are shown in Table 1.

[0023]

[Table 1] Table 1 陽 Cation exchange after hot water treatment Ability (meq / g) シ ロ キ サ ン Siloxane 1st 2nd 3rd 4th ───────── ─────────────────────────── Example 1 1 0.97 0.96 0.96 0.95 Example 2 2 0.97 0.96 0.95 0.93 Example 3 3 0.99 0.97 0.97 0.96 Comparative Example 1 4 0.59 0.30 0.23 0.11 Comparative Example 2 5 0.62 0. 33 0.21 0.10 Comparative Example 3 6 0.55 0.31 0.23 0.12 ─────────

As described above, a sulfonic acid group-containing alkoxysilane compound capable of forming a polymer siloxane matrix and a sulfonic acid group-containing alkoxysilane compound prepared by hydrolyzing and dehydrating and condensing an alkoxysilane compound capable of forming a polymer siloxane matrix. It has been found that the organic high molecular siloxane has almost no decrease in the amount of cation exchange as compared with the sulfonic acid group-containing organic high molecular siloxane prepared by another preparation method, and has extremely high water resistance.

[0025]

According to the present invention, a sulfonic acid group-containing organic high molecular siloxane having remarkably improved water resistance can be produced, and the range of application as a conventional desalting and solid acid catalyst can be expanded. Becomes

Claims (6)

[Claims] 1. A _{R a n SiX (4- n)} ( wherein n capable of forming a polymeric siloxane matrix is 1 to 3 integers, R _a carbon number having at least one or more sulfonic acid groups 1 to 15 or less hydrocarbon groups, X is at least one selected from the group consisting of alkoxy groups,
Si represents a silicon atom. At least one alkoxysilane compound having a sulfonic acid group represented by), R _{b n} SiX capable of forming a polymeric siloxane matrix
_(4-n) (wherein n is an integer of 0 or more and 3 or less, R _b is a hydrocarbon group having 1 or more and 20 or less, and X is at least one selected from the group consisting of alkoxy groups. Yes, Si
Represents a silicon atom. A method for producing a sulfonic acid group-containing organic high molecular siloxane, comprising hydrolyzing and dehydrating at least one of the alkoxysilane compounds represented by the formula (1). Wherein _{R a n SiX (4- n)} ( wherein n capable of forming a polymeric siloxane matrix is 1 to 3 integers, R _a carbon number having at least one or more sulfonic acid groups 1 to 15 or less hydrocarbon groups, X is at least one selected from the group consisting of alkoxy groups,
Si represents a silicon atom. At least one alkoxysilane compound having a sulfonic acid group represented by), R _{b n} SiX capable of forming a polymeric siloxane matrix
_(4-n) (wherein n is an integer of 0 or more and 3 or less, R _b is a hydrocarbon group having 1 or more and 20 or less, and X is at least one selected from the group consisting of alkoxy groups. Yes, Si
Represents a silicon atom. 2. The process according to claim 1, wherein the raw material mixture containing at least one of the alkoxysilane compounds represented by the formula) is hydrolyzed and dehydrated and condensed. 3. The method according to claim 1, wherein the sulfonic acid group is an aromatic sulfonic acid group. 4. The method according to claim 3, wherein the aromatic sulfonic acid group is a phenylsulfonic acid group. 5. The method according to claim 1, wherein the alkoxy group is a methoxy group, an ethoxy group, an n-propoxy group or an isopropoxy group. 6. A sulfonic acid group-containing organic high molecular siloxane produced by the production method according to claim 1. Description: