JPS6034573B2 - Method for producing organosilicon polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an organic poppy compound having high water repellency by reacting a siloxysilanol with an organosilylating agent.

Conventionally, organic poppy compounds produced by the reaction of siloxysilanol and organosilylating agents were produced under the Tokusekki Sho 51-12219.
As disclosed in Japanese Patent No. 8, siloxysilanol in an aqueous solution is extracted into an organic solvent using salt and is synthesized by reacting it with an organosilylating agent in the organic solution.

However, this method requires a complicated salting-out process;
It is difficult to dispose of the excess salt used in salting out, and the yield is greatly reduced due to the losses caused by such a complicated step. Since extraction is forced into an organic solvent layer by salting out, the extraction rate is poor, resulting in a low reaction rate and yield. On the other hand, in response to such a complicated method, Samurai Publication No. 49-4063y,
A method is described in which silanol is decomposed with hydrochloric acid in a solution prepared by adding trimethylcyclosilane to a water-soluble organic solvent without salting out, and trimethylation is simultaneously performed.
In this method, silanol is decomposed with hydrochloric acid in a solution prepared by adding trimethylchlorosilane to a water-insoluble organic solvent without salting out, and at the same time trimethylsilylation is carried out. In this method, there is no complicated process such as salting, but the organosilylating agent is dissolved in an organic solvent that is insoluble in water, while the siloxysilanol is dissolved in water.
The drawback is that contact between the two is restricted, and therefore the trimethylsilylation reaction is difficult to proceed and the yield is very low. The present invention was developed in order to eliminate various drawbacks of the above-mentioned known methods for producing organic poppy compounds, and aims to simplify the production method and increase the yield.

That is, the present invention involves reacting siloxysilanol obtained by acid decomposition of water glass or other poppy, acid salts or poppy or acid salt minerals with an organosilylating agent in a mixed solvent of water and a water-soluble organic solvent. Provided is a method for producing an organosilicon polymer comprising:

The water-soluble organic solvents used here include ethers,
Alcohols, ketones, etc. are used, and specific examples include methyl alcohol, ethyl alcohol, alcohol, and alcohol.

lopi/rare/record/shi, isopropylene alcohol,
Examples include acetone and methyl ether. Raw materials for siloxysilanol include water glass, other poppies, acid salts, poppy seeds, and acid salt minerals, such as JISI No., JI
S2, JIS No. 3 water glass, high molar ratio water glass (molar ratio 3.5-5.0), poppy, acid soda, ortholinic acid soda, peridotite, beryl, pyroxene group, argentite Zeolites such as mica, talc, tortuvite, benite, poppy, ashstone, ikiyoku key, soda stone and dafutsuite, soda stone, kifutsuite, albite, kaijiyujifu-) stone, etc. used.

Compounds represented by the following general formula are effective as organosilylating agents.

SIROX4-n Specific examples of these include trimethylchlorosilane, trimethylsilanol,
hexamethyldisiloxane, triethylchlorosilane,
Examples include triethylsilanol, dimethyldichlorosilane, diethyldichlorosilane, and 1,3-dichlorotetramethyldisiloxane.

Among these, trimethylchlorosilane, triethylchlorosilane and hexamethyldisiloxane are particularly preferred. The method of the invention is generally carried out as follows.

First, when water glass is used as a siloxysilanol source, siloxysilanol is prepared by adding an aqueous solution of water glass to a mineral acid at a predetermined concentration. In this case, p
H is preferably 3 or less. Next, a water-lacquer organic solvent is added to the siloxysilanol and mixed thoroughly, and an organosilylating agent is gradually added while stirring to cause a reaction. At this time, the water-bathable organic solvent may be mixed with the organosilylation agent in advance and then added to the siloxysilanol.
Alternatively, the organosilylating agent and the siloxysilanol may be mixed together in any proportion and then mixed together. Although the water-soluble organic solvent can be used in any amount to advance the reaction, it is preferably added in an amount of 30 to 50% of the total solution amount. Although the reason for this is not clear, siloxysilanols are hydrophobic and silylating agents are hydrophobic. Therefore, by adding a water-soluble organic solvent, the polarity of the aqueous solution is changed, increasing the dispersibility in both the siloxysilanol and the silylation agent, and increasing the reaction rate of both reagents. At this time, it is necessary to disperse both the elixirs at the same time, and the optimum value is 30 to 30% of the organic solvent amount.
It is estimated to be in the range of 50%. After the reaction is complete, the precipitated product is separated, washed with water and dried. in this case,
Immediately after the completion of the reaction, add a water-insoluble organic solvent and stir thoroughly to transfer the product into the water-insoluble organic solvent.
This layer may be dispersed, washed with water, and dried to obtain a product. According to the latter method, the product dispersed in the reaction system can also be recovered, so that the product can be obtained in higher yield. Examples of water-insoluble organic solvents include, but are not limited to, petroleum benzine, petroleum ether, benzene, toluene, and xylene. The product is a transparent resinous or glassy substance that is water repellent. Next, when poppy seeds and salt minerals are used as the siloxysilanol source, the poppy seeds and salt minerals are finely ground, added to a mixture of hydrochloric acid and a water-soluble organic solvent, and thoroughly stirred.

Next, an organosilylating agent is added and the reaction is allowed to proceed with sufficient lighting. The conditions for the water-soluble organic solvent and organosilylating agent at this time and the method for recovering the product after the reaction are the same as in the case of water glass. Note that the reaction between siloxysilanol and organosilylation agent is an exothermic reaction, but even at room temperature,
The reaction can also be carried out by heating or cooling. Since the organolenaline polymer obtained by the method of the present invention has lipophilicity and water repellency, it is particularly suitable for use as a water repellent agent, an antifoaming agent, a mold release agent, and the like.

Furthermore, according to the method of the present invention, steps such as salt folding are omitted, which not only simplifies the process and reduces costs, but also reduces losses in the manufacturing process and increases the yield by about 20% or more. An increase is seen. Furthermore, the yield is improved by 40% or more compared to the reaction method in a water-insoluble organic solvent.
Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 30% sulfuric acid 30% and 70% acetone are mixed, and 10% No. 3 Renso 40% Z is gradually added dropwise while stirring.

Next, 3.4 parts of trimethylchlorosilane was gradually added while stirring, and the mixture was stirred for about 1 hour. After the reaction is complete, add 50% of petroleum benzine and shake thoroughly. Next, the petroleum benzene layer was separated, washed with water, and dried to obtain a resinous product. The Si yield was about 82%. Example 2 The amount of acetone added was changed to 50' in the same manner as in Example 1.
And so.

The Si yield was about 70%. Example 3 The same method as in Example 1 was used, with the amount of acetone added being 30%.

The Si yield was about 65%. Example 4 The same method as in Example 1 was used, with the amount of acetone added being 18'.

The Si yield was about 43%. Comparative example 1 The production was carried out using a known method of salting out.

Gradually drop 40 parts of 10% No. 3 silica into 30% sulfuric acid and 30 parts of sulfuric acid. Immediately after dropping, add 60 tons of isopropanol and add sodium chloride while stirring until supersaturated. Separate the isopropanol layer using a separatory funnel, gradually add 3.4 liters of trimethylchlorosilane to it while stirring, and leave for about 1 hour. After the reaction is completed, the gel-like substance is purified with petroleum benzine and then washed with water to obtain a resin-like product. The Si yield was about 59%. Comparative Example 2 A known manufacturing method using a water-insoluble organic solvent was used.

Ice, hydrochloric acid, methanol, petroleum benzine, and trimethylchlorosilane at 10, 20, 40, and 30, respectively.
', 3.3 [Additionally, worship the fly for about 2 minutes. Next, a 15 M aqueous IM solution of No. 3 diatom was gradually added dropwise, and the mixture was left to stand for about 3 hours. Next, the organic solvent layer was separated, washed with water, and dried to obtain a resinous product. The Si yield was about 48%. Example 5 In the same manner as in Example 1, the amount of acetone added was about 105'.

The Si yield was about 50%. Example 6 The same method as in Example 1 was used, with the amount of acetone added being approximately 280°C.

The Sj yield was about 45%. Example 7 In the same manner as in Example 1, approximately 70 ml of inpropyl alcohol was added as a water-soluble organic solvent.

The Si yield was about 68%. Example 8 In the same manner as in Example 1, about 50% of ethyl alcohol was added as a water-lacquer organic solvent.

The Si yield was about 60%. Comparative Example 3 Acetone 60 was used as a polar organic solvent in the same manner as Comparative Example 1.
' was added.

The Si yield was about 60%. Table 1 summarizes the results of Examples 1 to 9 and Comparative Examples 1 to 3. Sj yield was determined by gravimetric method. Table-I The results of Table-1 are also shown as a graph in the attached drawing.

This shows that when the amount of organic solvent is 30 to 6% by weight, particularly 30 to 5% by weight, the Si yield increases. Example 9 In the same manner as in Example 1, the amount of acetone added was approximately 170°.

The Si yield was about 49%. Example 10 In the same manner as in Example 1, 2.8% of hexamethyldisiloxane was used as the organosilylation agent and 70% of acetone was used as the organic solvent.

The Si yield was about 76% (organic solvent/total solution 50%).
). Example 11 In the same manner as in Example 1, 2.8' of hexamethyldisiloxane was used as the organosilylating agent and 30' of acetone was used as the organic solvent.

The Si yield was about 60% (organic solvent/total solution 30%
). Example 12 In the same manner as in Example 1, 1,3 was used as an organosilylating agent.
-dichlorotetramethyldisiloxane (2.5%) and acetone (70%) as the organic solvent.

The Si yield was about 65% (organic solvent/total solution 50%
).

[Brief explanation of drawings]

The attached drawing is a graph showing the relationship between the amount of organic solvent and the Si yield.

Claims (1)

[Claims] 1. A method for producing an organosilicon polymer, which comprises reacting siloxysilanol in an aqueous solution system containing an organosilylating agent and a water-soluble organic solvent.