JP2006249160A - Sulfonated polyorganosilsesquioxane and its preparation method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sulfonated polyorganosilsesquioxane favorable for an antistatic for a plastic film, a dopant for a conductive polymer, a solid acid catalyst or an additive for a solid electrolyte membrane of a fuel cell. <P>SOLUTION: The sulfonated polyorganosilsesquioxane contains the structural unit (1) represented by R<SP>1</SP>-SiO<SB>3/2</SB>(wherein R<SP>1</SP>is a 1-3C alkyl group or a 2-3C alkenyl group), the structural unit (2) represented by Ph-SiO<SB>3/2</SB>and the structural unit (3) represented by HO<SB>3</SB>S-Ph-SiO<SB>3/2</SB>in a molar ratio of (1):(2):(3) of 0-99:0-99:1-100 (wherein (1)+(2)+(3) being 100), and the terminals of the polymer are -OR<SP>2</SP>(wherein R<SP>2</SP>are independently a 1-3C alkyl group or a hydrogen atom, provided that, when the structural unit (1) is not contained, the polymer has at least one terminal in which R<SP>2</SP>is a 1-3C alkyl group). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel sulfonated polyorganosilsesquioxane and a method for producing the same.

Synthesis of sulfonated PPSQ in which a sulfonic acid group is introduced into the phenyl group of polyphenylsilsesquioxane (hereinafter sometimes referred to as PPSQ) has been reported (see Patent Document 1).
French Patent Application No. 2669033

  However, according to the study by the present inventors, this sulfonated PPSQ is easily soluble in water. For this reason, there has been a problem that loss due to dissolution of the sulfonated PPSQ in water is large in washing with water in the purification stage or in an environment where water is present.

  Further, this sulfonated PPSQ does not have an alkoxy group which is a reactive group at the terminal. For this reason, when used as an additive for general-purpose resins, there is a problem in that a chemical bond with the matrix is difficult to form and the sulfonated PPSQ is detached from the matrix.

  As a result of intensive studies in view of the above-mentioned problems of the prior art, the present inventors have developed a new sulfone having a higher crosslinking density using a specific monomer and having an alkoxy group which is a reactive group at the terminal. It was found that a modified polyorganosilsesquioxane was obtained, and the present invention was completed.

That is, the present invention relates to the following sulfonated polyorganosilsesquioxane and a method for producing the same.
Item 1:
As a component,
General formula (1)

（式中、Ｒ¹は炭素原子数１〜３のアルキル基又は炭素原子数２〜３のアルケニル基である）で表される構造単位、
一般式（２）

(Wherein R ¹ is an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms),
General formula (2)

で表される構造単位及び一般式（３）

A structural unit represented by the general formula (3)

で表される構造単位を、（１）：（２）：（３）のモル比が０〜９９：０〜９９：１〜１００（但し（１）＋（２）＋（３）＝１００とする）の割合で含有し、ポリマーの末端が−ＯＲ²（Ｒ²は独立して炭素原子数１〜３のアルキル基又は水素原子である。但し、（１）の構造単位を含有しない場合、Ｒ²が炭素原子数１〜３のアルキル基である末端を少なくとも一個を有する。）であるスルホン化ポリオルガノシルセスキオキサン。
項２：
（１）：（２）：（３）のモル比が１〜９９：０〜９９：１〜９９である項１に記載のスルホン化ポリオルガノシルセスキオキサン。
項３：
Ｒ¹がメチル基又はビニル基である項２に記載のスルホン化ポリオルガノシルセスキオキサン。
項４：
一般式（４）

The molar ratio of (1) :( 2) :( 3) is 0 to 99: 0 to 99: 1 to 100 (provided that (1) + (2) + (3) = 100) And the terminal of the polymer is —OR ² (R ² is independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. However, when the structural unit of (1) is not contained, A sulfonated polyorganosilsesquioxane, wherein R ² has at least one terminal which is an alkyl group having 1 to 3 carbon atoms.
Item 2:
Item 2. The sulfonated polyorganosilsesquioxane according to Item 1, wherein the molar ratio of (1) :( 2) :( 3) is 1 to 99: 0 to 99: 1 to 99.
Item 3:
Item 3. The sulfonated polyorganosilsesquioxane according to item 2, wherein R ¹ is a methyl group or a vinyl group.
Item 4:
General formula (4)

（式中、Ｘは炭素原子数１〜３のアルコキシ基又は塩素原子である）
で表される化合物と、
一般式（５）

(Wherein X is an alkoxy group having 1 to 3 carbon atoms or a chlorine atom)
A compound represented by
General formula (5)

（式中、Ｙは炭素原子数１〜３のアルコキシ基又は塩素原子である）
で表される化合物と、
一般式（６）

(In the formula, Y is an alkoxy group having 1 to 3 carbon atoms or a chlorine atom)
A compound represented by
General formula (6)

（式中、Ｒは炭素原子数１〜３のアルキル基又は炭素原子数２〜３のアルケニル基であり、Ｚは炭素原子数１〜３のアルコキシ基又は塩素原子である）
で表される化合物とを共加水分解縮合して、
構成成分として、一般式（１）

(In the formula, R is an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, and Z is an alkoxy group having 1 to 3 carbon atoms or a chlorine atom.)
Co-hydrolytic condensation with a compound represented by
As a component, the general formula (1)

（式中、Ｒ¹は炭素原子数１〜３のアルキル基又は炭素原子数２〜３のアルケニル基である）で表される構造単位、
一般式（２）

(Wherein R ¹ is an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms),
General formula (2)

で表される構造単位及び一般式（３）

A structural unit represented by the general formula (3)

で表される構造単位を、（１）：（２）：（３）のモル比が１〜９９：０〜９９：１〜９９（但し（１）＋（２）＋（３）＝１００とする）の割合で含有し、ポリマーの末端が−ＯＲ²（Ｒ²は独立して炭素原子数１〜３のアルキル基又は水素原子である）であるスルホン化ポリオルガノシルセスキオキサンの製造方法。
項５：
Ｒ¹がメチル基又はビニル基である項４に記載のスルホン化ポリオルガノシルセスキオキサンの製造方法。
項６：
一般式（４）

The molar ratio of (1) :( 2) :( 3) is 1 to 99: 0 to 99: 1 to 99 (provided that (1) + (2) + (3) = 100) And a terminal of the polymer is —OR ² (R ² is independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom), and a method for producing a sulfonated polyorganosilsesquioxane. .
Item 5:
Item 5. The method for producing a sulfonated polyorganosilsesquioxane according to Item 4, wherein R ¹ is a methyl group or a vinyl group.
Item 6:
General formula (4)

（式中、Ｘは炭素原子数１〜３のアルコキシ基又は塩素原子である）
で表される化合物と、
一般式（５）

(Wherein X is an alkoxy group having 1 to 3 carbon atoms or a chlorine atom)
A compound represented by
General formula (5)

（式中、Ｙは炭素原子数１〜３のアルコキシ基又は塩素原子である）
で表される化合物とを（但しＸ及びＹのうちの少なくとも一つは炭素原子数１〜３のアルコキシ基である）、
（４）及び（５）の合計量に対し０．０１モル倍〜１．５モル倍の水の存在下で共加水分解することを特徴とする、
構成成分として、
一般式（２）

(In the formula, Y is an alkoxy group having 1 to 3 carbon atoms or a chlorine atom)
(Wherein at least one of X and Y is an alkoxy group having 1 to 3 carbon atoms),
Co-hydrolyzing in the presence of 0.01 mol times to 1.5 mol times water relative to the total amount of (4) and (5),
As a component,
General formula (2)

で表される構造単位及び一般式（３）

A structural unit represented by the general formula (3)

で表される構造単位を、（２）：（３）のモル比が０〜９９：１〜１００（但し（２）＋（３）＝１００とする）の割合で含有し、ポリマーの末端が−ＯＲ²（Ｒ²は独立して炭素原子数１〜３のアルキル基又は水素原子である。但し、Ｒ²が炭素原子数１〜３のアルキル基である末端を少なくとも一個を有する。）であるスルホン化ポリオルガノシルセスキオキサンの製造方法。

The molar ratio of (2) :( 3) is 0 to 99: 1 to 100 (provided that (2) + (3) = 100), and the polymer ends are —OR ² (R ² is independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, provided that R ² has at least one terminal which is an alkyl group having 1 to 3 carbon atoms). A method for producing a sulfonated polyorganosilsesquioxane.

Hereinafter, the present invention will be described in detail.
1. Sulfonated polyorganosilsesquioxane The sulfonated polyorganosilsesquioxane of the present invention has the following components:
General formula (1)

（式中、Ｒ¹は炭素原子数１〜３のアルキル基又は炭素原子数２〜３のアルケニル基である）で表される構造単位、
一般式（２）

(Wherein R ¹ is an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms),
General formula (2)

で表される構造単位及び一般式（３）

A structural unit represented by the general formula (3)

で表される構造単位を、（１）：（２）：（３）のモル比が０〜９９：０〜９９：１〜１００（但し（１）＋（２）＋（３）＝１００とする）の割合で含有し、ポリマーの末端が−ＯＲ²（Ｒ²は独立して炭素原子数１〜３のアルキル基又は水素原子である。但し、（１）の構造単位を含有しない場合、Ｒ²が炭素原子数１〜３のアルキル基である末端を少なくとも一個を有する。）である。

The molar ratio of (1) :( 2) :( 3) is 0 to 99: 0 to 99: 1 to 100 (provided that (1) + (2) + (3) = 100) And the terminal of the polymer is —OR ² (R ² is independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. However, when the structural unit of (1) is not contained, R ² has at least one terminal which is an alkyl group having 1 to 3 carbon atoms.

In the general formula (1), R ¹ is an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, preferably a methyl group or a vinyl group.

  In the sulfonated polyorganosilsesquioxane of the present invention, the general formula (3) is an essential constituent, and the constituents of the general formulas (1) and (2) are optional constituents. The composition ratio of these components is (1) 0 to 99: (2) 0 to 99: (3) 1 to 100 in terms of a molar ratio where the sum of (1), (2) and (3) is 100. Preferably, (1) 1 to 99: (2) 0 to 99: (3) 1 to 99, more preferably (1) 10 to 80: (2) 0 to 80: (3) 10 90, and more preferably (1) 30 to 80: (2) 0 to 50: (3) 20 to 60.

Furthermore, the terminal structure of the sulfonated polyorganosilsesquioxane of the present invention is —OR ² (R ² is independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, provided that (1) When it does not contain a structural unit, R ² has at least one terminal which is an alkyl group having 1 to 3 carbon atoms.), And preferred R ² is a methyl group or an ethyl group.

The sulfonated polyorganosilsesquioxane of the present invention includes, for example, at least one repeating unit having a structure represented by the following general formulas (7) to (9), and further includes the following general formulas (10) and (11 And a polymer containing at least one end of the structure represented by
General formula (7)

一般式（８）

General formula (8)

一般式（９）

General formula (9)

一般式（１０）

General formula (10)

一般式（１１）

Formula (11)

（式(7)〜(11)中、Ｒ¹¹，Ｒ¹²、Ｒ¹³，Ｒ¹⁴はそれぞれ独立してスルホフェニル基、炭素原子数１〜３のアルキル基、炭素原子数２〜３のアルケニル基、フェニル基を示す。Ｒ²¹、Ｒ²²はそれぞれ独立して炭素原子数１〜３のアルキル基又は水素原子を示す。）
本発明のスルホン化ポリオルガノシルセスキオキサンは、例えばプラスチックフィルムの帯電防止剤、導電性高分子のドーパント、固体酸触媒又は燃料電池の固体電解質膜の添加剤として有用である。

(In the formulas (7) to (11), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a sulfophenyl group, an alkyl group having 1 to 3 carbon atoms, and an alkenyl group having 2 to 3 carbon atoms. And R ²¹ and R ²² each independently represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom.)
The sulfonated polyorganosilsesquioxane of the present invention is useful, for example, as an antistatic agent for plastic films, a dopant for conductive polymers, a solid acid catalyst, or an additive for solid electrolyte membranes in fuel cells.

2. Method 1 for producing sulfonated polyorganosilsesquioxane
The method for producing the sulfonated polyorganosilsesquioxane of the present invention includes:
General formula (4)

（式中、Ｘは炭素原子数１〜３のアルコキシ基又は塩素原子である）
で表される化合物と、
一般式（５）

(Wherein X is an alkoxy group having 1 to 3 carbon atoms or a chlorine atom)
A compound represented by
General formula (5)

（式中、Ｙは炭素原子数１〜３のアルコキシ基又は塩素原子である）
で表される化合物と、
一般式（６）

(In the formula, Y is an alkoxy group having 1 to 3 carbon atoms or a chlorine atom)
A compound represented by
General formula (6)

（式中、Ｒは炭素原子数１〜３のアルキル基又は炭素原子数２〜３のアルケニル基であり、Ｚは炭素原子数１〜３のアルコキシ基又は塩素原子である）
で表される化合物と
を共加水分解縮合することを特徴とする。この製造方法を製造方法１と称することがある。ここで、一般式（４）、（５）及び（６）で表される化合物は、その各原料製造過程において、あるいは本発明の製造過程において、その加水分解物および／又はその初期縮合物を生成する場合があるが、本発明においては、これら一般式（４）、（５）及び（６）で表される化合物には、それらの加水分解物および／又はその初期縮合物が含まれていても良く、これらの各化合物、その加水分解物およびその初期縮合物の単独又はこれらの混合物であっても良い。以下同じ。

(In the formula, R is an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, and Z is an alkoxy group having 1 to 3 carbon atoms or a chlorine atom.)
It is characterized by cohydrolytic condensation with a compound represented by This manufacturing method may be referred to as manufacturing method 1. Here, the compounds represented by the general formulas (4), (5) and (6) are produced by the hydrolysis and / or initial condensate thereof in the respective raw material production processes or in the production process of the present invention. In the present invention, these compounds represented by the general formulas (4), (5) and (6) include their hydrolyzate and / or initial condensate thereof. Each of these compounds, a hydrolyzate thereof, and an initial condensate thereof may be used alone or as a mixture thereof. same as below.

The sulfonated polyorganosilsesquioxane produced by this production method is
As a component, the general formula (1)

（式中、Ｒ¹は炭素原子数１〜３のアルキル基又は炭素原子数２〜３のアルケニル基である）で表される構造単位、
一般式（２）

(Wherein R ¹ is an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms),
General formula (2)

で表される構造単位及び一般式（３）

A structural unit represented by the general formula (3)

で表される構造単位を、（１）：（２）：（３）のモル比が１〜９９：０〜９９：１〜９９（但し（１）＋（２）＋（３）＝１００とする）の割合で含有し、ポリマーの末端が−ＯＲ²（Ｒ²は独立して炭素原子数１〜３のアルキル基又は水素原子である）である。すなわち、この製造方法によって製造されるスルホン化ポリオルガノシルセスキオキサンは、一般式（１）で表される構造単位及び一般式（３）で表される構造単位を必須の構造とし、一般式（２）で表される構造単位を任意の構造単位として含む。

The molar ratio of (1) :( 2) :( 3) is 1 to 99: 0 to 99: 1 to 99 (provided that (1) + (2) + (3) = 100) The terminal of the polymer is —OR ² (R ² is independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom). That is, the sulfonated polyorganosilsesquioxane produced by this production method has the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3) as an essential structure, The structural unit represented by (2) is included as an arbitrary structural unit.

In the production method of the present invention, preferable ones of R ¹ , R ² , X, Y, Z and R in the general formulas (1) to (6) and —OR ² are those described in “1. Sulfonated polyorganosilsesquioxy”. As described in “Sun”.

  Specific examples of the compound represented by the general formula (4) include sulfophenyltrichlorosilane, sulfophenyltrimethoxysilane, sulfophenyltriethoxysilane, sulfophenyltripropoxysilane, sulfophenyltriisopropoxysilane and the like.

  The compound represented by the general formula (4) can be produced, for example, by the following method. For example, phenyltrichlorosilane is charged into an organic solvent such as 1,2-dichloroethane or methylene chloride, and a sulfonating agent such as chlorosulfonic acid or sulfuric anhydride is added thereto to remove the generated hydrogen chloride from the system. Is obtained as an organic solvent solution of sulfonated phenyltrichlorosilane. The addition amount of the sulfonating agent is usually about 0.1 to 1.0 mol times with respect to phenyltrichlorosilane. Moreover, it can also be set as sulfonated phenyl trialkoxysilane by dripping excess alcohol to the obtained sulfonated phenyltrichlorosilane and alkoxylating the sulfonated phenyltrichlorosilane.

  Specific examples of the compound represented by the general formula (5) include phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, and phenyltriisopropoxysilane.

  Specific examples of the compound represented by the general formula (6) include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, Ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltriisopropoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, Vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxy Silane, allyl tripropoxysilane, and the like allyl triisopropoxysilane is.

  As described above, the compounds represented by the general formulas (4), (5) and (6) may contain a hydrolyzate and an initial condensate thereof, that is, the general formulas (4), ( The chlorine and / or alkoxy groups of the compounds represented by 5) and (6) are hydrolyzed to form hydroxyl groups, and the hydroxyl groups are condensed to form the initial condensate. In the manufacturing method of this invention, each of these compounds, its hydrolyzate, and its initial condensate may be included individually or in mixture.

  In the production method of the present invention, the compound represented by the general formula (4) is used as an essential raw material, and the compounds represented by the general formulas (5) and (6) are arbitrarily used as raw materials according to a desired object, These are cohydrolyzed and condensed. The usage-amount of each raw material can be suitably set according to the ratio of the structural component contained in desired sulfonated polyorganosilsesquioxane. For example, the usage amount of each raw material with respect to the total amount of the compounds represented by the general formulas (4), (5), and (6) is as follows. The usage-amount of the compound represented by General formula (4) is 1-99 mol% normally, Preferably it is 10-90 mol%, More preferably, it is 20-60 mol%. The usage-amount of the compound represented by General formula (5) is 0-99 mol% normally, Preferably it is 0-80 mol%. The usage-amount of the compound represented by General formula (6) is 1-99 mol% normally, Preferably it is 10-90 mol%. In addition, when using a hydrolyzate or an initial condensate as a raw material, these usage-amounts are the quantity from which the quantity converted into the monomer becomes said range.

  In the production method of the present invention, these raw materials are cohydrolyzed and condensed. The conditions for cohydrolytic condensation are not particularly limited as long as these raw materials are hydrolyzed and condensed. For example, these raw materials are mixed in an organic solvent, the organic solvent is added dropwise to water, and if necessary, cohydrolytic condensation can be performed by stirring. Here, examples of the organic solvent include saturated or unsaturated aliphatic hydrocarbons and their halides (for example, hexane, heptane, cyclohexane, chloroform, dichloromethane, 1,2-dichloroethane, etc.), aromatic hydrocarbons and their halogens. (E.g., benzene, toluene, xylene, chlorobenzene, dichlorobenzene, etc.), ether compounds (e.g., diethylene glycol dimethyl ether, tetrahydrofuran, etc.), ester compounds (e.g., ethyl acetate, propyl acetate, butyl acetate, etc.), nitrogen compounds (e.g., N, N'-dimethylformamide, acetonitrile, etc.), carbonyl compounds such as ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) and the like, preferably 1,2-di Is Roroetan. The usage-amount of an organic solvent is 0.5-100 weight times normally with respect to the total amount of these raw materials, Preferably it is 2-10 weight times. In addition, when not using an organic solvent, it can co-hydrolyze-condense by dripping these raw material mixtures to water.

  In the co-hydrolysis condensation, the amount of water is usually 3 mol times or more, preferably 10 to 500 mol times, more preferably 50 to 150 mol times with respect to the total amount of the above raw materials. The temperature of cohydrolysis condensation is usually 0 to 100 ° C, preferably 10 to 40 ° C, more preferably 15 to 25 ° C. The cohydrolysis condensation time is not particularly limited as long as the desired product can be produced, but is usually 30 minutes or longer, preferably 1 to 10 hours, more preferably 2 to 5 hours.

  Even after the completion of dropping of the organic solvent containing the raw material mixture into water, the cohydrolysis condensation reaction may be advanced by stirring as necessary.

  After completion of the reaction, the organic solvent is removed from the system by a method such as distillation, and a sulfonated polyorganosilsesquioxane can be obtained by filtration, washing with water and drying under reduced pressure as necessary. Moreover, after removing an organic solvent out of a system, it can obtain also in order of filtration, reduced pressure drying, water washing, and reduced pressure drying processing. When the content of the sulfonic acid group of the target product is relatively high, the organic solvent is preferably removed from the system, and then treated in the order of filtration, drying under reduced pressure, washing with water and drying under reduced pressure. Although the temperature of vacuum drying is not specifically limited, It is 50-200 degreeC, Preferably it is 100-150 degreeC.

3. Method 2 for producing sulfonated polyorganosilsesquioxane
Furthermore, the method for producing the sulfonated polyorganosilsesquioxane of the present invention includes:
General formula (4)

（式中、Ｘは炭素原子数１〜３のアルコキシ基又は塩素原子である）
で表される化合物と、
一般式（５）

(Wherein X is an alkoxy group having 1 to 3 carbon atoms or a chlorine atom)
A compound represented by
General formula (5)

（式中、Ｙは炭素原子数１〜３のアルコキシ基又は塩素原子である）
で表される化合物とを（但しＸ及びＹのうちの少なくとも一つは炭素原子数１〜３のアルコキシ基である）、
（４）及び（５）の合計量に対し０．０１モル倍〜１．５モル倍の水の存在下で共加水分解することを特徴とする。この製造方法を製造方法２と称することがある。

(In the formula, Y is an alkoxy group having 1 to 3 carbon atoms or a chlorine atom)
(Wherein at least one of X and Y is an alkoxy group having 1 to 3 carbon atoms),
Co-hydrolysis is carried out in the presence of 0.01 mol times to 1.5 mol times of water relative to the total amount of (4) and (5). This manufacturing method may be referred to as manufacturing method 2.

The sulfonated polyorganosilsesquioxane produced by this production method is
As a component,
General formula (2)

で表される構造単位及び一般式（３）

A structural unit represented by the general formula (3)

で表される構造単位を、（２）：（３）のモル比が０〜９９：１〜１００（但し（２）＋（３）＝１００とする）の割合で含有し、ポリマーの末端が−ＯＲ²（Ｒ²は独立して炭素原子数１〜３のアルキル基又は水素原子である）である。すなわち、この製造方法によって製造されるスルホン化ポリオルガノシルセスキオキサンは、一般式（３）で表される構造単位を必須の構造とし、一般式（２）で表される構造単位を任意の構造単位として含む。

The molar ratio of (2) :( 3) is 0 to 99: 1 to 100 (provided that (2) + (3) = 100), and the polymer ends are —OR ² (R ² is independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom). That is, the sulfonated polyorganosilsesquioxane produced by this production method has the structural unit represented by the general formula (3) as an essential structure and the structural unit represented by the general formula (2) as an arbitrary structure. Included as a structural unit.

In the production method 2 of the present invention, preferable R ² , X and Y in the general formulas (2) to (5) are as described in “1. Sulfonated polyorganosilsesquioxane”. Moreover, at least one of X and Y in the compounds of the general formulas (4) and (5) is an alkoxy group having 1 to 3 carbon atoms. Further, examples of the compounds of the general formulas (4) and (5) are as described in the above-mentioned “2. Production method 1 of sulfonated polyorganosilsesquioxane”. Examples and amounts of organic solvents used in the cohydrolytic condensation are also as described in “2. Production method 1 of sulfonated polyorganosilsesquioxane”.

  In the production method 2 of the present invention, the compound represented by the general formula (4) is used as an essential raw material, and the compound represented by the general formula (5) is arbitrarily used as a raw material in accordance with a desired object, and these are used together. Hydrolytic condensation. The usage-amount of each raw material can be suitably set according to the ratio of the structural component contained in desired sulfonated polyorganosilsesquioxane. For example, the amount of each raw material used with respect to the total amount of the compounds represented by the general formulas (4) and (5) is as follows. The usage-amount of the compound represented by General formula (4) is 1-100 mol% normally, Preferably it is 10-90 mol%, More preferably, it is 20-60 mol%. The usage-amount of the compound represented by General formula (5) is 0-99 mol% normally, Preferably it is 10-90 mol%.

  In the production method 2 of the present invention, these raw materials are cohydrolyzed and condensed, but the amount of water is important. The amount of water to be used is usually 0.01 mol times to 1.5 mol times, preferably 0.5 mol times to 1.1 mol times with respect to the total amount of the general formulas (4) and (5). When the amount of water is within this range, it is advantageous from the viewpoint of production of a target product containing an alkoxy group at the terminal.

  Other conditions for the cohydrolysis condensation and the treatment after the cohydrolysis condensation are as described in “2. Production method 1 of sulfonated polyorganosilsesquioxane”.

  The sulfonated polyorganosilsesquioxane of the present invention has a relatively low solubility in water, such as an antistatic agent for plastic films, a dopant for conductive polymers, a solid acid catalyst, or an additive for solid electrolyte membranes in fuel cells. Useful.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. The sulfonation rate is a percentage of the number of components of the general formula (3) with respect to the total number of components of the general formulas (1), (2), and (3).

Synthesis example 1
A 1 liter flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 152.0 g (718.5 mmol) of phenyltrichlorosilane and 750 g of 1,2-dichloroethane (hereinafter sometimes abbreviated as EDC). While maintaining the reaction mixture at 10 ° C. or lower, 75.21 g (645.41 mmol, phenyltrichlorosilane / chlorosulfonic acid = 100/90 molar ratio) of chlorosulfonic acid was added dropwise under a nitrogen environment to remove hydrogen chloride from the system. While removing, the mixture was heated to reflux for 5 hours. The reaction solution was cooled to room temperature to obtain 939.4 g of an EDC solution of sulfonated phenyltrichlorosilane.

Example 1
116.9 g of EDC solution of sulfonated phenyltrichlorosilane obtained in Synthesis Example 1 (containing a total of 89.4 mmol of sulfonated phenyltrichlorosilane and phenyltrichlorosilane) was added 40.1 g (268.2 mmol) of methyltrichlorosilane. The resulting mixture (methyltrichlorosilane / sulfonated phenyltrichlorosilane and phenyltrichlorosilane total amount = 3/1 mol ratio) was added dropwise to 600.0 g water at 15-20 ° C. and stirred at room temperature for 4 hours. Subsequently, EDC was removed by distillation, filtered, washed with water, and dried under reduced pressure at 100 ° C. for 6 hours to obtain 34.4 g of white powdered sulfonated polyphenylmethylsilsesquioxane (yield: 90.8%). ). The results are shown in Table 1.
The sulfonation rate by elemental analysis of this sulfonated polyphenylmethylsilsesquioxane was 20.3%. Further, when infrared absorption spectrum analysis was measured, the absorption attributed to Si—CH ₃ was 1274 cm ⁻¹ , the absorption attributed to Si—C ₆ H ₅ was 1430 cm ⁻¹ , and Si—O—Si Since absorption attributed to stretching vibration was observed at 1037 cm ⁻¹ and 1135 cm ⁻¹ , it was identified as the structure of polyphenylmethylsilsesquioxane. The infrared absorption spectrum is shown in FIG.

Comparative Example 1
116.7 g of EDC solution of sulfonated phenyltrichlorosilane obtained in Synthesis Example 1 (containing 89.4 mmol of the total amount of sulfonated phenyltrichlorosilane and phenyltrichlorosilane) was added 56.7 g (268.2 mmol) of phenyltrichlorosilane. Other than addition, it carried out similarly to Example 1, and obtained 38.7g of white powdery sulfonated polyphenylsilsesquioxane (yield: 65.3%). The sulfonation rate of this sulfonated polyphenylmethylsilsesquioxane by elemental analysis was 4.2%. The results are shown in Table 1.

Example 2
13.3 g (89.4 mmol) of methyltrichlorosilane was added to 116.9 g of EDC solution of sulfonated phenyltrichlorosilane obtained in Synthesis Example 1 (containing a total of 89.4 mmol of sulfonated phenyltrichlorosilane and phenyltrichlorosilane). The resulting mixture (methyltrichlorosilane / sulfonated phenyltrichlorosilane and phenyltrichlorosilane total amount = 1/1 molar ratio) was added dropwise to 600.0 g of water at 15 to 20 ° C. and stirred at room temperature for 4 hours. did. Subsequently, EDC was removed by distillation, filtered, and dried under reduced pressure at 100 ° C. for 6 hours to obtain 23.0 g of powdered sulfonated polyphenylmethylsilsesquioxane. The obtained sulfonated polyphenylmethylsilsesquioxane was washed with water to remove residual impurities, and dried under reduced pressure at 100 ° C. for 6 hours to obtain 21.7 g of powdered sulfonated polyphenylmethylsilsesquioxane (recovery). Rate: 73.5%). The sulfonation rate of this sulfonated polyphenylmethylsilsesquioxane by elemental analysis was 30.0%. The results are shown in Table 1.

Comparative Example 2
116.9 g (89.4 mmol) of phenyltrichlorosilane was added to 116.9 g of the EDC solution of sulfonated phenyltrichlorosilane obtained in Synthesis Example 1 (containing 89.4 mmol of the total amount of sulfonated phenyltrichlorosilane and phenyltrichlorosilane). Other than addition, it carried out similarly to Example 2, and obtained white powdery sulfonated polyphenylsilsesquioxane 17.8g (yield: 41.5%). The sulfonation rate of this sulfonated polyphenylsilsesquioxane by elemental analysis was 3.8%. The results are shown in Table 1.

Synthesis example 2
A 1 liter flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 750 g of EDC and 151.1 g (714.4 mmol) of phenyltrichlorosilane, and then kept in a nitrogen environment while keeping the reaction mixture at 10 ° C. or lower. 33.3 g of chlorosulfonic acid (285.7 mmol, 40 mol% with respect to phenyltrichlorosilane) was added dropwise, and the mixture was heated to reflux for 5 hours while removing hydrogen chloride from the system. The reaction solution was cooled to room temperature to obtain an EDC solution of a brown uniform liquid sulfonated phenyltrichlorosilane. Then, EDC was distilled off by concentration under reduced pressure to obtain 180.6 g of brown liquid sulfonated phenyltrichlorosilane.

  Ethanol 196.3 g (4.261 mol) was dropped into the sulfonated phenyltrichlorosilane thus obtained over 2 hours while removing hydrogen chloride from the system at 10 to 25 ° C. under a nitrogen stream, followed by 2 at room temperature. Ethoxylation was carried out with stirring for a period of time. Then, it concentrated under reduced pressure at 70-78 degreeC, ethanol was distilled off, and 190.0g (yield: 97.8%) of sulfonated phenyltriethoxysilane and phenyltriethoxysilane mixture was obtained.

Example 3
A 500 mL flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 200 g of toluene and 22.0 g (80.88 mmol) of the sulfonated phenyltriethoxysilane and phenyltriethoxysilane mixture obtained in Synthesis Example 2, followed by 1.601 g of water (88.97 mmol, total amount of sulfonated phenyltriethoxysilane and phenyltriethoxysilane: water = 1: 1.1 molar ratio) was added dropwise to obtain a mixed solution at room temperature for 1 hour at 100 ° C. For 2 hours. Then, it concentrated under reduced pressure and dried under reduced pressure at 100 ° C. for 4 hours to obtain 14.9 g of a powdered terminal ethoxy group-containing sulfonated polyphenylsilsesquioxane. (Yield: 96.0%).
When this terminal ethoxy group-containing sulfonated polyphenylsilsesquioxane was reacted with excess water and the ethanol formed was analyzed by gas chromatography (GC), the terminal ethoxy group content (definition of ethoxy content: terminal ethoxy) In the group-containing sulfonated polyphenylsilsesquioxane condensate, the molar ratio of ethoxy groups to Si atoms was 6.0%. Further, the sulfonation rate of this terminal ethoxy group-containing sulfonated polyphenylsilsesquioxane by elemental analysis was 36.8%. The results are shown in Table 2.

Example 4
A 500 mL flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 200 g of toluene and 22.0 g (80.88 mmol) of the sulfonated phenyltriethoxysilane and phenyltriethoxysilane mixture obtained in Synthesis Example 2, followed by 1.601 g of water (88.97 mmol, total amount of sulfonated phenyltriethoxysilane and phenyltriethoxysilane: water = 1: 1.1 molar ratio) was added dropwise, and the resulting mixture was stirred at room temperature for 3 hours. Then, it concentrated under reduced pressure at 40 degreeC and dried under reduced pressure at 40 degreeC for 4 hours, and obtained 15.0g of powdery terminal ethoxy group containing sulfonated polyphenylsilsesquioxane. (Yield: 95.4%).
When this terminal ethoxy group-containing sulfonated polyphenylsilsesquioxane was reacted with excess water and the ethanol formed was analyzed by gas chromatography (GC), the terminal ethoxy group content was 10.0%. The sulfonation rate of this terminal ethoxy group-containing sulfonated polyphenylsilsesquioxane by elemental analysis was 35.6%. The results are shown in Table 2.

Comparative Example 3
A 500 mL flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 200 g of toluene and 22.0 g (80.88 mmol) of the sulfonated phenyltriethoxysilane and phenyltriethoxysilane mixture obtained in Synthesis Example 2, followed by 4.367 g of water (242.61 mmol, total amount of sulfonated phenyltriethoxysilane and phenyltriethoxysilane: water = 1: 3 molar ratio) was added dropwise to obtain a mixed solution obtained at room temperature for 1 hour and at 100 ° C. for 2 hours. Stir for hours. Then, it concentrated under reduced pressure and dried under reduced pressure at 100 ° C. for 4 hours to obtain 12.1 g of powdered sulfonated polyphenylsilsesquioxane. (Yield: 93.0%).
When this sulfonated polyphenylsilsesquioxane was reacted with excess water and analyzed by gas chromatography (GC), ethanol was not detected and the terminal ethoxy group content was 0%. The sulfonation rate of this sulfonated polyphenylsilsesquioxane by elemental analysis was 33.5%. The results are shown in Table 2.

  The sulfonated polyorganosilsesquioxane of the present invention is useful as an antistatic agent for plastic films, a dopant for conductive polymers, a solid acid catalyst or an additive for solid electrolyte membranes in fuel cells.

1 shows the infrared absorption spectrum of the sulfonated polyphenylmethylsilsesquioxane obtained in Example 1. FIG.

Claims (6)

As a component,
General formula (1)

(Wherein R ¹ is an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms),
General formula (2)

A structural unit represented by the general formula (3)

The molar ratio of (1) :( 2) :( 3) is 0 to 99: 0 to 99: 1 to 100 (provided that (1) + (2) + (3) = 100) And the terminal of the polymer is —OR ² (R ² is independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. However, when the structural unit of (1) is not contained, A sulfonated polyorganosilsesquioxane, wherein R ² has at least one terminal which is an alkyl group having 1 to 3 carbon atoms. The sulfonated polyorganosilsesquioxane according to claim 1, wherein the molar ratio of (1) :( 2) :( 3) is 1 to 99: 0 to 99: 1 to 99. The sulfonated polyorganosilsesquioxane according to claim 2, wherein R ¹ is a methyl group or a vinyl group. General formula (4)

(Wherein X is an alkoxy group having 1 to 3 carbon atoms or a chlorine atom)
A compound represented by
General formula (5)

(In the formula, Y is an alkoxy group having 1 to 3 carbon atoms or a chlorine atom)
A compound represented by
General formula (6)

(In the formula, R is an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, and Z is an alkoxy group having 1 to 3 carbon atoms or a chlorine atom.)
Co-hydrolytic condensation with a compound represented by
As a component, the general formula (1)

(Wherein R ¹ is an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms),
General formula (2)

A structural unit represented by the general formula (3)

The molar ratio of (1) :( 2) :( 3) is 1 to 99: 0 to 99: 1 to 99 (provided that (1) + (2) + (3) = 100) And a terminal of the polymer is —OR ² (R ² is independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom), and a method for producing a sulfonated polyorganosilsesquioxane. . The method for producing a sulfonated polyorganosilsesquioxane according to claim 4, wherein R ¹ is a methyl group or a vinyl group. General formula (4)

(Wherein X is an alkoxy group having 1 to 3 carbon atoms or a chlorine atom)
A compound represented by
General formula (5)

(In the formula, Y is an alkoxy group having 1 to 3 carbon atoms or a chlorine atom)
(Wherein at least one of X and Y is an alkoxy group having 1 to 3 carbon atoms),
Co-hydrolyzing in the presence of 0.01 mol times to 1.5 mol times water relative to the total amount of (4) and (5),
As a component,
General formula (2)

A structural unit represented by the general formula (3)

The molar ratio of (2) :( 3) is 0 to 99: 1 to 100 (provided that (2) + (3) = 100), and the polymer ends are —OR ² (R ² is independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, provided that R ² has at least one terminal which is an alkyl group having 1 to 3 carbon atoms). A method for producing a sulfonated polyorganosilsesquioxane.

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