JP2914868B2 - Method for producing organopolysiloxane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an SiO ₂ unit (hereinafter referred to as Q
It is called a unit. The present invention relates to a method for producing an organopolysiloxane having a specific reactive organic group, and more particularly to a method for producing an organopolysiloxane having a specific reactive organic group.

[0002]

2. Description of the Related Art A benzene-soluble compound having _0.5 units of R ₃ SiO (where R is a hydrogen atom or a monovalent hydrocarbon group; such units are hereinafter referred to as M units) and further having Q units. Are widely used in the silicone field. The organopolysiloxane has, for example, the following general formula: R _a SiX _(4-a) (where R is as described above, X is an alkoxy group or a hydroxyl group, and a is an integer of 1 to 3) ) And an organosilane represented by the following formula: R _b SiO _{(4-b) / 2} (where R is as described above and b is an integer of 1 to 3). A method comprising reacting an organopolysiloxane containing units with an alkyl silicate or a partial hydrolysis product thereof in the presence of at least one acidic catalyst selected from the group consisting of sulfonic acid group-containing compounds and phosphonitrile chloride. It is manufactured (see Japanese Patent Publication No. 4-26609).

[0003]

However, in the above-mentioned method, since an acidic catalyst is used as a catalyst, it has a Q unit according to the above-mentioned method, and for example, an amino group, a mercapto group, an acryloxy group, etc. Even when trying to produce an organopolysiloxane containing a reactive organic group having,
The production is difficult because the acidic catalyst reacts with the reactive organic group.

Accordingly, an object of the present invention is to have a Q unit,
Amino group, mercapto group, acryloxy group , methacryloyl
At least one selected from the group consisting of xy and epoxy groups
Another object of the present invention is to provide a method for producing an organopolysiloxane containing a reactive organic group having one kind of functional group.

[0005]

Means for Solving the Problems The present inventors have made intensive studies on a method for producing an organopolysiloxane having a Q unit and containing the above-mentioned specific reactive organic group. As a result, an alkoxy group or a hydroxyl group was obtained. And an organosilane having a reactive organic group containing an amino group, a mercapto group, an acryloxy group, and the like, and an organosilane having an alkoxy group or a hydroxyl group, without a catalyst, or under a basic catalyst. It was found that when the reaction was carried out, condensation was caused by a dehydration or dealcoholation reaction, and the present invention was completed.

The present invention relates to (A) (a) an alkyl silicate having an SiO ₂ unit, a partial hydrolyzate thereof, or a combination thereof, and (b) the following formula (1): (R ¹ ) _a SiO ₍₄ ) _{-a) / 2} (1) wherein R ¹ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and a is an integer of 1 to 3. (C) reacting with an organosiloxane in the presence of at least one acidic catalyst selected from the group consisting of a sulfonic acid group-containing compound and phosphonitrile chloride, and (d) water; (A) neutralizing the acidic catalyst contained in the reaction mixture obtained in (A), (C) the reaction mixture neutralized in the above step (B), (e) the following general formula (2): R ¹ ) _b (R ² ) _c SiX _(4-bc) (2) (wherein, when a plurality of R ¹ are present, they may be the same or different. It is as, if R ² there exist a plurality they may be the same or different, amino
Group, mercapto group, acryloxy group, methacryloxy group
And at least one selected from the group consisting of epoxy groups
Is a monovalent reactive organic group having 1 to 6 carbon atoms having a functional group represented by the formula: when there are a plurality of Xs, they may be the same or different and each is an alkoxy group or a hydroxyl group;
And c is an integer of 1 to 3, provided that 1
≦ b + c ≦ 3. ) And a step of reacting a organosilane represented by having a SiO ₂ units, the
Provided is a method for producing an organopolysiloxane containing a specific reactive organic group.

[0007] (a) used in the component (a) of the present invention the alkyl silicate and partial hydrolysis products thereof of the components are those having a Q unit. The content of the Q unit is not particularly limited, and is preferably in the range of 20 to 50% by weight, and more preferably 37 to 50% by weight.
It is in the range of 48% by weight. As such a component (a),
Conventionally known ones can be used, and examples thereof include alkyl silicates such as orthomethyl silicate, polymethyl silicate, orthoethyl silicate, polyethyl silicate, orthopropyl silicate, and polypropyl silicate, and partial hydrolysis products thereof. Can be

(B) Component The organosiloxane of the component (b) has a unit represented by the above formula (1). The component has M units, (R ¹ )
Supply ₂ SiO units (D units) and / or R ¹ SiO _3/2 units (T units).

R ¹ in the above formula (1) is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include those having 1 to 8 carbon atoms. No. Specific examples of R ¹ include an alkyl group such as a methyl group, an ethyl group, a propyl group and an n-butyl group; an alkenyl group such as a vinyl group, a propenyl group and a butenyl group; Examples thereof include aryl groups such as a benzyl group and a naphthyl group.

As the organosiloxane of the component (b),
Conventionally known materials are used, and specific examples thereof include hexamethyldisiloxane, 1,3-diethyl-1,1,3,3-tetramethyldisiloxane, and octamethyltrisiloxane. Component (b) may be used alone or
Used in combinations of more than one species.

Component (c) Component (c) is at least one catalyst selected from the group consisting of sulfonic acid group-containing compounds and phosphonitrile chloride, and promotes the reaction between components (a) and (b). Is what you do.

The sulfonic acid group-containing compound includes:
For example, sulfuric acid, sulfurous acid, fuming sulfuric acid, paratoluenesulfonic acid, acid clay, activated clay, trifluoromethanesulfonic acid, solid superacid and the like can be mentioned.

The amount of component (c) added is preferably in the range of 0.001 to 3% by weight of the total amount of components (a) and (b).

The amount of component water added is preferably in the range of 0.6 to 1.5 moles, and more preferably 0.8 to 1.5 moles per mole of alkoxy group contained in component (a) and component (e) described below. It is preferably in the range of ~ 1.2 mol. If the amount of water is too large, the number of remaining hydroxyl groups increases, and it becomes difficult to control the molecular weight. On the other hand, if the amount of water is too small, a large amount of alkoxy groups in the alkyl silicate as the component (a) will remain.

(E) Component The organosilane as the component (e) is represented by the above general formula (2). (e) The component is added to the target organopolysiloxane.
Used to introduce the above specific reactive organic groups.
M units, D units, and / or T units are supplied as constituent units.

[0016] R ² in the general formula (2) is amino group, a mercapto group, an acryloxy group, methacryloxy group and Et
A monovalent reactive organic group having 1 to 6 carbon atoms and having a functional group selected from the group consisting of a oxy group ;
Aminopropyl group, acryloxypropyl group, mercaptopropyl group, main Taku Lilo carboxyethyl group, aminoethyl group, etc. γ- glycidoxypropyl groups.

X in the general formula (2) is an alkoxy group or a hydroxyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a propenoxy group and a butoxy group. Among them, an ethoxy group and a propoxy group are preferred.

Examples of the organosilane (e) include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, Acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, aminopropyldimethylmethoxysilane, γ-mercaptopropylmethyldimethoxysilane, acryloxypropylmethyldimethoxysilane , γ-glycidoxy
Propyltrimethoxysilane and the like. above
(b) The above (a) based on the amount of the component organosiloxane
The total added amount of the component and the component (e) depends on the molar ratio of the other units M, D, and T contained in the organopolysiloxane having the desired Q unit, and the molecular weight distribution. What is necessary is just to adjust suitably.

Step (A) In the step (A), the alkyl silicate and / or its partial hydrolysis product of the component (a) and the organosiloxane of the component (b) are combined with the catalyst of the component (c). (d) The reaction is carried out in the presence of water as a component and in an appropriate organic solvent, if necessary. This reaction is usually performed in a reactor equipped with a rectification tube. The reaction is usually performed at a temperature in the range of 40 to 80 ° C.

The organic solvent used if necessary includes, for example, hydrocarbon solvents such as hexane, octane, toluene, and benzene;
Examples include ether solvents such as tetrahydrofuran and dioxane, and among them, hexane and toluene are preferred.

Step (B) In the step (B), the reaction mixture obtained in the above step (A) is
For example, it is neutralized by a basic compound such as a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide or a bicarbonate such as sodium bicarbonate. If the neutralization is insufficient, it is further neutralized with a weakly basic compound such as sodium carbonate.

Step (C) The reaction mixture neutralized in the above step (B) is added to the above (e)
By dropping the component, for example, by performing a reaction with an ester trap, having the target SiO ₂ unit,
An organopolysiloxane containing the specific reactive organic group can be produced. The reaction is usually between 110 and 14
It is performed in the range of 0 ° C.

Further, the reaction of step (C) is performed under acidic catalyst, since the a reactive organic group and an acidic catalyst reacts carried out in the absence of a catalyst or under a basic catalyst, preferably And under a basic catalyst. Examples of the basic catalyst include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide. When the reaction is carried out in the presence of a basic catalyst, it is preferable that the reaction is neutralized with sodium carbonate, magnesium carbonate, calcium carbonate, potassium carbonate, citric acid or the like after completion of the reaction.

According to the present invention, by controlling the amount of the components (a) to (e) added, the reaction temperature, and the reaction time, the amount of alkoxy groups remaining in the organopolysiloxane having the desired Q unit can be adjusted. Since the amount of hydroxyl groups and the molecular weight distribution can be adjusted, various organopolysiloxanes can be easily produced.

Further, according to the present invention, since hydrochloric acid is not produced as a by-product, there is an advantage that it is not necessary to take measures against corrosion of the reactor.

[0026]

Next, the present invention will be described specifically with reference to examples. Example 1 162.4 g (1.0 mol) of hexamethyldisiloxane was mixed with ethyl silicate 40 (trade name, manufactured by Tama Chemical Industry Co., Ltd., SiO ₂ unit 40).
150.0g (1mol as SiO ₂ unit) and concentration 98%
2 g of concentrated sulfuric acid was added. While stirring the resulting mixture, 36 g of water was added dropwise at 0 to 20 ° C over 1 hour. Next, one hour after the completion of the dropwise addition, reflux (80 ° C.) was started, and the mixture was stirred for 5 hours. The resulting reaction mixture was neutralized with sodium bicarbonate. After the neutralization was completed, 179 g (1 mol) of γ-aminopropyltrimethoxysilane was added to the reaction mixture, and a reaction was carried out for 6 hours while removing by-produced methanol and ethanol using an ester trap tube. After completion of the reaction, the obtained reaction solution was prepared in a 50% by weight toluene solution of an organosiloxane. Thus, 315 g (95% yield) of the organopolysiloxane was obtained.

Next, when the organopolysiloxane was analyzed, [(CH ₃ ) ₃ SiO _0.5 ] unit, H ₂ N (CH ₂ )
It was confirmed that the composition contained _1.5 SiO ₃ units and ₃ SiO ₂ units in a molar ratio of 1: 1: 1.

Example 2 46.6 g (0.25 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and hexamethyldisiloxane 4
0.6 g (0.25 mol), ethyl silicate 40 150.0 g (SiO ₂
1 mol) and 5 g of p-toluenesulfonic acid were added. While stirring the obtained mixture, 1 g of water was added at 0 to 20 ° C with 1 g of water.
It was dropped over time. Next, one hour after the completion of the dropping, 35 g of water was added, reflux (80 ° C.) was started, and stirring was performed for 5 hours. The resulting reaction mixture was neutralized with sodium bicarbonate. After completion of the neutralization, 98.2 g (0.5 mol) of γ-mercaptopropyltrimethoxysilane was added to the reaction mixture, and a reaction was carried out for 6 hours while removing by-produced methanol and ethanol using an ester trap tube. After the reaction,
The obtained reaction liquid was prepared as a 50% by weight toluene solution of organosiloxane. Thus, 263 g (95% yield) of the organopolysiloxane was obtained.

Next, when the organopolysiloxane was analyzed, [(CH ₂ = CH) (CH ₃ ) ₂ SiO _0.5 ] units,
It was confirmed that the composition contained [(CH ₃ ) ₃ SiO _0.5 ] units, HS (CH ₂ ) ₃ SiO _1.5 units and SiO ₂ units in a molar ratio of 0.25: 0.25: 1: 0.5.

Example 3 To 162.4 g (1.0 mol) of hexamethyldisiloxane, 150.0 g of ethyl silicate 40 (1 mol as SiO ₂ unit) and 2 g of 98% concentrated sulfuric acid were added. While the resulting mixture was stirred, 24 g of water was added dropwise at 0 to 20 ° C over 1 hour. Next, one hour after the completion of dropping, reflux (80 ° C.) was started, and stirring was performed for 5 hours. The resulting reaction mixture was neutralized with sodium bicarbonate. After the neutralization was completed, 236.3 g (1 mol) of γ-glycidoxypropyltrimethoxysilane was added to the reaction mixture, and a reaction was carried out for 6 hours while removing by-produced methanol and ethanol using an ester trap tube. . After the reaction,
The obtained reaction liquid was prepared as a 50% by weight toluene solution of organosiloxane. Thus, 370 g (95% yield) of the organopolysiloxane was obtained.

Then, when the organopolysiloxane was analyzed, [(CH ₃ ) ₃ SiO _0.5 ] unit, the following formula:

[0032]

Embedded image

It was confirmed that the unit contained the unit represented by the formula and the SiO ₂ unit in a molar ratio of 1: 1: 1.

Example 4 To 93.2 g (0.5 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added 152 g of tetramethoxysilane (1 mol).
mol) and 5 g of p-toluenesulfonic acid, and 9 g of water was added dropwise at 0 to 20 ° C over 1 hour while stirring the resulting mixture. One hour after the completion of the dropwise addition, 35 g of water was added, reflux (80 ° C.) was started, and the mixture was stirred for 5 hours. The resulting reaction mixture was neutralized with sodium bicarbonate. After completion of the neutralization, 98.2 g (0.5 mol) of γ-mercaptopropyltrimethoxysilane was added to the reaction mixture, and the mixture was reacted for 6 hours while removing by-produced methanol and ethanol using an ester trap tube. After completion of the reaction, the obtained reaction solution was prepared in a 50% by weight toluene solution of an organosiloxane. Thus, 263 g (95% yield) of the organopolysiloxane was obtained.

Next, when this organopolysiloxane was analyzed, the molar ratio of [(CH ₂ = CH) (CH ₃ ) ₂ SiO _0.5 ] unit, HS (CH ₂ ) ₃ SiO _1.5 unit and SiO ₂ unit was determined.
It was confirmed that the content was 0.5: 0.5: 0.5: 1.

Example 5 To 93.2 g (0.5 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added 208 g (1 mol) of tetraethoxysilane.
mol) and 5 g of p-toluenesulfonic acid, and 9 g of water was added dropwise at 0 to 20 ° C over 1 hour while stirring the resulting mixture. One hour after the completion of the dropwise addition, 35 g of water was added, reflux (80 ° C.) was started, and the mixture was stirred for 5 hours. The resulting reaction mixture was neutralized with sodium bicarbonate. After the neutralization was completed, 117 g (0.5 mol) of acryloxypropyltrimethoxysilane and 1.0 g of a 50% aqueous potassium hydroxide solution were added to the reaction mixture, and methanol and ethanol by-produced were removed using an ester trap tube. After completion of the reaction, the resulting reaction solution was neutralized with 0.6 g of citric acid to prepare a 50% by weight toluene solution of an organosiloxane. Thus, 273 g of organopolysiloxane (yield 90
%)was gotten.

Then, when this organopolysiloxane was analyzed, [(CH ₂ = CH) (CH ₃ ) ₂ SiO _0.5 ] unit, the following formula:

[0038]

Embedded image

The unit represented by the formula and the SiO ₂ unit are in a molar ratio
It was confirmed that the content was 0.5: 0.5: 0.5: 1.

[0040]

According to the present invention, an organopolysiloxane having a Q unit and containing a reactive organic group can be easily produced. The organopolysiloxane can be used, for example, in combination with a catalyst, a dye, etc., due to its adhesion aid to various sealing agents, and its excellent weather resistance, electrical insulation, etc., for industrial plants, heating appliances, furnaces, household ranges. It is useful for paints and the like.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08G 77/06 C08G 77/388 C08G 77/392

Claims (2)

(57) [Claims] (A) (a) an alkyl silicate having an SiO ₂ unit, a partial hydrolyzate thereof, or a combination thereof, and (b) the following formula (1): (R ¹ ) _a SiO _{(4-a ) / 2} (1) (wherein, R ¹ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and a is an integer of 1 to 3). Reacting in the presence of (c) at least one acidic catalyst selected from the group consisting of a sulfonic acid group-containing compound and phosphonitrile chloride, and (d) water; and (B) the step (A) (C) neutralizing the acidic catalyst contained in the reaction mixture obtained in (C), (C) the reaction mixture neutralized in the step (B), and (e) the following general formula (2): (R ^{1 _{) b (R 2) c SiX}} (4-bc) (2) ( wherein, in as they said may be the same or different when R ¹ there are a plurality of Ri, when R ² there exist a plurality they may be the same or different, amino
Group, mercapto group, acryloxy group, methacryloxy group
And at least one selected from the group consisting of epoxy groups
Is a monovalent reactive organic group having 1 to 6 carbon atoms having a functional group represented by the formula: when there are a plurality of Xs, they may be the same or different and each is an alkoxy group or a hydroxyl group;
And c is an integer of 1 to 3, provided that 1
≦ b + c ≦ 3. ) And a step of reacting a organosilane represented by having a SiO ₂ units, the manufacturing method of the organopolysiloxane containing the <br/> reactive organic groups. 2. The organopolysiloxane according to claim 1.
A method for producing a catalyst, wherein the reaction of the step (C) is a basic catalyst.
A method performed in the presence of a medium.