JPS5827808B2 - Manufacturing method of polyorganosiloxane resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for stably and efficiently producing a fast-curing polyorganosiloxane resin.

In the production of polyorganosiloxane resins, the average compositional formula is selected from the group consisting of halosilanes and organohalosilanes. , n is 0
．． Indicates a number from 5 to 1.7.

Q[-+Waterlysis or co-hydrolysis of single or mixed silanes resulting in Q[--The straw method is common.

In this case, if the reaction is carried out vigorously, the produced polyorganosiloxane resin will be unstable due to the produced hydrogen halide, and the condensation reaction between the silanol groups will proceed, forming a gel-like product. This makes them unsuitable for most applications of polyorganosiloxane resins, such as coil impregnation, mica bonding, and laminate formation.

In addition, as a result of such a condensation reaction, the silanol group content of the polyorganosiloxane/powder resin decreases, making it unsuitable for applications requiring rapid curing.

Therefore, the reaction has traditionally been controlled by silanes and/or hydrolysis → [1] by making organic solvents such as toluene or xylene exist, or by making alcohols such as impropatol or butanol coexist. In this way, a polyorganosiloxane resin solution in which an appropriate amount of silanol groups and alkoxy groups remain is formed.

For example, Special Publication No. 46-4-1396, Special Publication No. 48146
No. 80 proposes that a fast-curing polyorganosiloxane resin can be stabilized by using acetone and alcohol in addition to a water-insoluble organic solvent.

However, this method requires the use of large amounts of water and organic solvents, which has the disadvantage of significantly reducing the efficiency of the reactor.

Furthermore, it is extremely difficult to recover, purify, and reuse the used organic solvent.

Furthermore, the polyorganosiloxane resin obtained by this method has a wide molecular weight distribution, so it does not have sufficient flowability during molding and has poor solvent resistance when used as a paint. Since this method requires a considerably large amount of water, there is a problem that the efficiency of the device is further reduced.

U.S. Pat. No. 3,262,830 and U.S. Pat. No. 3,304,318 disclose that using alkoxysilanes such as organol-IJ alkoxysilane as a starting material, a titanium compound or a sulfonic acid-based ion exchange resin is added to the alkoxy group. By reacting 0.5 to 1 mol of water, alkoxysilanes are hydrolyzed and condensed,
It is proposed to obtain a laminate 1-tl of polyorganosiloxane resin.

Furthermore, US Pat. No. 3,389,114 similarly proposes that organotrialkoxysilane is partially hydrolyzed in the presence of a trace amount of hydrogen chloride to obtain a solid ripe-curable polyorganosiloxane resin. There is.

However, in these methods, a large amount of amines, such as pyridine, must be added to remove the hydrogen halide produced when the necessary organo-IJ alkoxysilane is obtained by alkoxylation of organotrihalosilane. However, it requires an additional step to remove the fine crystals of the amine-hydrogen halide double salt that is produced, which is unfavorable in terms of equipment efficiency and complexity of work.
If these steps are omitted, the alkoxysilanes have poor stability and form a gel during storage.

In addition, in the case of the former method, the content of silanol groups in the obtained polyorganosiloxane is small, and for example, after heating at 110°C for 25 minutes,
A good laminate cannot be obtained unless pressurization and heating are carried out for a total of 45 minutes at C, and in the case of the latter straw method,
The stability and curability of the resin are affected by the small amount of hydrogen chloride added, and it is difficult to control this.

Furthermore, in Japanese Patent Publication No. 46-37740, in the hydrolysis of organotrihalosilane, a large amount of methyldialkoxydihalosilane obtained by once alkoxylating two halogen atoms in one molecule and a small amount of methyl l-IJ alkoxysilane are disclosed. or a mixture with phenyl 1-
A straw method has been proposed in which a mixture with added lyhalosilane is co-hydrolyzed with water.

However, in this method, the concentration of hydrogen halide generated by hydrolysis of the remaining silicon-bonded halogen atoms is high, so the bonding of the polyorganosiloxane progresses, and only a product with few silanol groups and poor reactivity is obtained. do not have.

Furthermore, in JP-A-50-77500, organohalosilane is reacted with alcohol and water to produce an alkoxylated organohalosiloxane in which 5 to 40 weight percent of silicon functional groups are alkoxy groups, and further alcohol A method has been proposed in which the acidity of the alkoxylated organohalosiloxane is adjusted to 1 to 300 pI)m, and water is added to hydrolyze the alkoxylated organohalosiloxane.

However, in this method, the manufacturing process is complicated, and in particular, the time required to use the equipment for removing acid components is long, and the obtained polyorganosiloxane resin is not quick-curing.

The present invention controls the amount of hydrogen halide remaining in the alkoxysilanes by once reacting silanes with alcohols to form alkoxysilanes, and removing the generated hydrogen halide from the system by heating. The object of the present invention is to provide a method for producing a polyorganosiloxane resin having fast curing properties, solvent resistance, and compatibility with organic resins in a stable manner and with efficient equipment by subsequently performing hydrolysis.

That is, the present invention provides an average compositional formula of R, S I X4 n (wherein R1,
In a method for producing a polyorganosiloxane resin starting from a single or mixed silane (X and n are as described above), (a) the silane is converted into a halogen atom 11 bonded to the silicon atom; Per hard 0.9
~20 mol of alcohol represented by the general formula R20H (wherein R2 represents a monovalent group having 1 to 8 carbon atoms selected from an alkyl group and an alkyloxyethyl group), (b) The resulting argyl silicate and alkoxysilanes selected from the group consisting of organoalkoxysilanes are heated to a temperature above 70°C so that the remaining amount of hydrogen halide becomes below 3 weight ZJy. Continue heating until (C) 10-2000-200p of alkoxysilanes
(d) react with at least enough stoichiometric water to completely hydrolyze and condense the alkoxysilanes to form a polyorganosiloxane; (e) leave the production system still; to separate the acid and water mixture from the polyorganosiloxane layer, (f) add water and heat to a temperature of 60 to 1000C to remove the acid, and then (g) remove water and further as necessary te (h) (
By repeating steps f) and Q), the amount of hydrogen halide in the polyorganosiloxane resin was reduced to 1 ppr.
The present invention relates to a method for producing a polyorganosiloxane resin, which is characterized in that the polyorganosiloxane resin is reduced to below ++J,a.

The silanes used in the present invention have an average compositional formula of R15i.
A halogen atom is bonded to a silicon atom to form X3 (where R1, X and n are as described above), and may be a single atom or a mixture thereof.

RISiX3 alone or R15iX3 and R,'5iX
2 is generally used, but 5iX4 (X is a halogen atom) may also be used in combination to obtain a harder film.

Further, R'3SiX may also be used in part.

R1 is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, an alkenyl group such as a vinyl group or an allyl group, a cycloalkyl group such as a cyclohexyl group, or a phenyl group. Examples include aryl groups such as benzyl groups, aralkyl groups such as styrenyl groups, monovalent substituted hydrocarbon groups such as trifluoropropyl groups, and chlorophenyl groups. In terms of hardness and ease of obtaining raw materials, a combination of methyl and phenyl groups or a methyl group is preferred.

As the halogen atom, a chlorine atom is preferred because of its easy availability and ease of removal in step (b).

The alcohol used in step (a) has 1 to 8 carbon atoms, and if the number of carbon atoms is larger than this, the reactivity during hydrolysis decreases and the alcohol becomes solid, making handling inconvenient.

Examples include monohydric unsubstituted alcohols such as methanol, ethanol, impropatol, n-butanol, and imbuknol, and ether alcohols such as methoxyethanol, ethoxyethanol, and butoxyethanol. may be used together.

Methanol, ethanol, or improper tool is preferable in view of the reactivity of the alkoxysilane produced, the ability to obtain an appropriate reflux temperature in step (b), and ease of handling.

The amount of alcohol is 0.9 to 2.0 mol, preferably 10 mol per silicon-bonded halogen atom of the silane.
~1.2 mol.

This is because if the amount of alcohol is less than this range, a large amount of silicon-halogen bonds will remain, and if the amount of alcohol is too large, the efficiency of the device will deteriorate.

The reaction method generally involves dropping an organohalosilane or a mixture of an organohalosilane and a halosilane into an alcohol, but it is also possible to drop an alcohol into the silane.

In this case, a portion of the alkoxysilane produced in step (a) undergoes partial hydrolysis and condensation due to the water in the alcohol and the water produced by the reaction between the by-produced hydrogen halide and the alcohol. However, the progress of the present invention cannot be overstated.

The heating in step (b) is to remove hydrogen halides from the generated alkoxysilanes.
Heating humidity above 0°C is required.

In this case, it is practical to heat the alkoxysilane and/or the remaining alcohol under reflux conditions, and the heating temperature varies depending on the type of alkoxysilane, but
Preferably, the temperature is between 0 and 120°C.

The heating time is set so that the amount of hydrogen halide remaining in the alkoxysilane layer does not exceed 3 weights, and is preferably between 20 and 120 minutes.

If the hydrogen halide concentration is higher than this, condensation of the polyorganosiloxane will occur in the hydrolysis step (d), making it impossible to obtain the desired polyorganosiloxane resin with a high content of silanol groups.

Further, it is preferable that the hydrogen halide concentration not be lowered to less than 0.5" by weight.

When the concentration of hydrogen chloride is below this level, the progress of the condensation reaction in the hydrolysis step of step (d) slows down,
This is because it is difficult to obtain solid resin for molding materials.

In addition, in order to lower the hydrogen halide concentration, addition of a trace amount of aqueous alkaline solution may be used in combination with the heating in step (b).

(c) The solvent added in the step is substantially incompatible with water and is a hydrocarbon such as benzene, toluene, xylene, petroleum ether, petroleum benzine, gasoline, naphtha, cyclohexane, methyldichlorohexane, ethylcyclohexane. Examples include chloroethylene-based solvents, /'% halogenated hydrocarbon-based solvents such as trichloroethylene, tetrachloroethylene, and chlorobenzene, ester-based solvents such as butyl acetate, and mixtures thereof.

The amount of such water-insoluble solvent added is 10 to 200% by weight, preferably 50% by weight of the alkoxysilane.
~150 weight.

If the amount of the water-insoluble solvent is less than this range, the condensation reaction of polyol and nosiloxane in the hydrolysis step of step (d) will proceed, resulting in a decrease in the amount of silanol groups in the polyorganosiloxane resin produced, and , the molecular weight distribution becomes broader.

Moreover, not only is the polyorganosiloxane resin layer and the aqueous layer not smoothly separated in steps (e) and (f), but the condensation reaction also proceeds during the separation after step (d), which is undesirable.

Furthermore, if the amount of water-insoluble solvent is too large, the efficiency of the apparatus will deteriorate.

In step (d), water may be added to the alkoxysilanes, or conversely, the alkoxysilanes may be added to water, but the alkoxysilanes obtained through steps (b) and (c) The most practical method is to add water dropwise to a similar solution while stirring.

While hydrolyzing alkoxysilanes with water,
A moderate condensation reaction is performed to form a polyorganosiloxane resin.

Therefore, the amount of water added must be at least equal to the amount of water consumed in this hydrolysis reaction minus the amount of water produced during the condensation reaction, and in addition, the amount of water that is In order to control the progress of the condensation reaction using hydrogen chloride as a promoter and form a polyorganosiloxane resin having an appropriate amount of silanol groups, it is preferable to add an excessive amount of water. In the case of methylisopropoxysilane, 15 to 5
It is in the range of 0 weight.

Although the time for adding water in step (d) is arbitrary, it is preferably a short time in order to prevent the condensation reaction from proceeding.

Although the temperature may be room temperature, heating or cooling, it is preferably under 60' CIJ in order to control the progress of the condensation reaction.

Then, in step (e), the aqueous layer is separated from the polyorganosiloxane resin layer by standing.

Here, a considerable amount of hydrogen halides and alcohols are transferred to the water layer and removed, but in order to further remove the hydrogen halides remaining in the polyorganosiloxane resin layer,
(f) Add water and heat under reflux to 60-100°C, preferably 70-90°C to transfer hydrogen halide to the aqueous layer, (g) leave to stand to separate and remove the aqueous layer. ,moreover(
h) By repeating steps (g) and (f) as necessary, the residual amount in the polyorganosiloxane resin can be
The amount of hydrogen halogenide is lppmJa or less, preferably 0.1
pl'1m, decrease ty until G is reached.

The amount of water in step (f) is not particularly limited, but from the viewpoint of cleaning effect and equipment efficiency, it is preferably 50 to 200 times the weight of the polyorganosiloxane layer separated in step (e).

If the heating temperature is lower than 60°C, the removal of hydrogen halides will not proceed easily, and if the heating temperature is higher than 100°C, condensation will proceed, which is not preferable.

A reflux time of 20 minutes is sufficient for some parts.

If the amount of hydrogen halide remaining in the polyorganosiloxane resin is not sufficiently reduced, the stability of the resin will deteriorate.

If necessary, (i) the water-insoluble solvent and remaining alcohol can be removed from the polyorganosiloxane resin by heating to obtain a solid or solid solvent-free polyorganosiloxane resin.

The polyorganosiloxane resin thus obtained has a narrow molecular weight distribution and a silanol group content of 7 to 1.
5 weight, which is higher than the conventional method (Koyoru).

Therefore, it has desirable properties as a resin for impregnation, mica adhesion, glass laminates, molding materials, and an intermediate for coatings, namely, rapid hardening, solvent resistance, and compatibility with organic resins.

Furthermore, when compared to resins made using methyltrichlorosilane as a starting material, less smoke is generated when heated to high temperatures, compared to resins produced by conventional methods.

The present invention provides a terra method for producing the above polyorganosiloxane resin safely, stably, and efficiently using equipment. The polyorganosiloxane resin obtained by the present invention can be used for impregnation, It is useful as a resin for mica adhesives, glass laminates, molding materials, and as an intermediate for paints.

Below, the present invention will be explained by way of examples.

In Examples and Comparative Examples, all parts represent parts by weight.

In addition, all information such as concentration is expressed in percent by weight.

Example 1 320 parts of methanol was charged into a reactor equipped with a stirrer, a condenser, a pressure reducer, and a thermometer, and 500 parts of methyltrichlorosilane was added dropwise over 40 minutes while stirring.

The reaction temperature was raised from 25°C to 60°C by -L,
The temperature dropped to 40'C with the release of hydrogen chloride gas.

The mixture was then gradually heated to 90° C. and heated with stirring for an additional 30 minutes to remove hydrogen chloride.

The concentration of hydrochloric acid in the methyl 1-rimethoxysilane produced by the reaction was 2.5.

The mixture was cooled to room temperature, and 400 parts of toluene was added thereto to obtain a toluene solution of methyl 1-rimethoxysilane.

While stirring this, 350 parts of water was added dropwise over 30 minutes.

The temperature rose to 40°C.

After the dropwise addition was completed, the temperature was raised to 75° C. and refluxed with stirring for 30 minutes.

Then, heating and stirring were stopped, and the mixture was allowed to stand for 15 minutes to remove the acidic aqueous layer.

Next, 500 parts of water was added, heated and refluxed at a temperature of 70°C for 30 minutes, and allowed to stand for 30 minutes to remove the lower aqueous layer.

The hydrochloric acid content of the produced polymethylsiloxane resin is 0.
], it was below ppmJy.

Next, a part of the solvent was stripped at a temperature of 40'C and an air pressure of 50 mmH, and the resin concentration was adjusted to 50%, and one filtration was performed to obtain a 50% toluene solution A1 of polymethylsiloxane resin.

The obtained A1 was put into a desolvation device equipped with a stirrer, a condenser, a pressure reducer, and a thermometer, and heated for 150 minutes under reduced pressure.
C. to completely remove the solvent.

The obtained polymethylsiloxane resin A2 has a softening point of 80
It was a friable solid at °C.

For comparison, a comparative sample was prepared as follows.

That is, 1500 parts of water, 500 parts of isopropanol,
A hydrolyzing agent consisting of 450 parts of acetone was charged into a reactor, and a mixture of 500 parts of methyltrichlorosilane and 600 parts of toluene was added to the reactor while stirring, and the temperature of the reactor was raised to 50°C by cooling.
Hydrolysis and condensation were carried out by dropping the mixture over a period of 1 hour while keeping the temperature at a lower temperature.

Stirring was continued for an additional 15 minutes, then left to stand for 10 minutes, and the acidic aqueous layer was removed.

Next, 500 parts of water was added and refluxed using the Terra method similar to the present invention.
Separation, dehydration, and concentration adjustment were performed to obtain a 50% toluene solution B1 of polymethylsiloxane resin, and further solvent removal was performed to obtain polymethylsiloxane resin B2.

B2 was a solid with a softening point of 60°C.

Resin A2. B2 was dissolved in a solvent with a weight ratio of toluene:ethanol of 7:3, respectively, to make a solution surface with a solid content of 2.5%,
The molecular weight distribution was measured using a gel permeation chromatography device ALC/CPC502 manufactured by Watersassociates using toluene as a standard solution.

Figure 1 shows the outflow curve of resin A.
is 4oO~4ooo1 Resin B2 Ka2 400~20000, and looking from the outflow curve,
It was found that resin B2 had large peaks in the low molecular weight region and the high molecular weight region.

Further, the nosilanol group contents of resin A2+B2 were measured and were 1], 3%, and 6.7%, respectively.

To examine the drying properties of resin solutions A□ and B1,
Add 0.5% iron octylate (8% iron content) to the resin content, and hot-play 1 at 150°C.
The gelation time was measured above.

While the resin solution A1 gelled in 5 minutes, the comparison sample bait fat solution B gelled in 15 minutes.

Resin A2. When each of B2 was crushed and stored at a temperature of 40° Ca for one month, resin A2 remained in a powder state, but resin B2 was found to have fused into a single piece.

This shows that 11fl'&A2 swords are easy to use as raw materials for powder coatings and molding materials.

64 parts of silica powder is added to 35 parts each of resins A1 and B1.
．． 5 parts of aluminum stearate and 0.5 parts of aluminum stearate were added, uniformly kneaded with two rolls heated to 100°C, and ground with a Henschel mixer to prepare powder coatings A3 and B3.

Apply this powder coating to a steel panel with a film thickness of 100 to 200.
Becomes μ-Yo-J-coating-C-2-Changing curing conditions-
The samples were cured and their hardness, solvent resistance, heat resistance and volume resistivity were measured.

The measurement results are shown in Table 1. Example 2 600 parts of isopropanol was charged into the same reactor as used in Example 1 (with underside), and 500 parts of methyltrichlorosilane was added dropwise over 40 minutes while stirring.

The reaction temperature rose once from 20°C to 60°C, and then fell to 35°C with the release of hydrogen chloride gas.

The mixture was then gradually heated to 100° C. and further heated with stirring for 30 minutes to remove hydrogen chloride.

The concentration of hydrochloric acid in the orgasoalkoxysilane produced by the reaction was 25%.

After cooling to room temperature, 600 parts of xylene was added to obtain a xylene solution of organoalkoxysilane.

While stirring this, 100 parts of water was added dropwise over 10 minutes.

The temperature rose to 45°C. After the dropwise addition was completed, the temperature was raised to 78° C. and refluxed with stirring for 10 minutes.

Then, heating and stirring were stopped, and the mixture was allowed to stand for 15 minutes to remove the acidic aqueous layer.

Next, 500 parts of water was added, heated and refluxed at a temperature of 78°C for 30 minutes, and left to stand for 15 minutes to remove the lower aqueous layer.

Furthermore, 500 parts of water was added and heated for 30 minutes at a temperature of 78°C.
It was refluxed for a minute and left to stand for 15 minutes to remove the lower aqueous layer.

The hydrochloric acid content of the produced polymethylsiloxane resin is 0.
It was below lppm1.

Next, adjust the concentration in the same manner as in Example 1※※ 50% xylene solution of polymethylsiloxane resin
I got 1.

20 each of the obtained C1 and comparative sample B1 of Example 1
53 parts of toluene and 27 parts of isopropanol were added to make a solution with a resin content of 10%, and to this was added 0.6% phosphoric acid based on the resin content as a hardening agent and 0.6% phosphoric acid based on the resin content as an additive. Binders C2 and B4 were prepared by adding 0.2% γ-(β-aminoethylamino)propyltrimethoxysilane.

Each of these binders was applied to the composite mica, and
A silicone mica laminate was obtained by drying at °C for 5 minutes, under a molding pressure cuff of 5 kg/cm, and changing the molding temperature and time as shown in Table 2.

The bending test values and volume resistivity of the obtained silicone mica laminate are shown in Table 2.

Incidentally, the silicone mica laminate made of the polysiloxane resin of the present invention hardly emitted smoke when heated to 600 to 700°C, but smoke was observed in the laminate made of the comparative sample.

Example 3 610 parts of Improper Tool was charged into a reactor, and a silane blend consisting of 157 parts of methyltrichlorosilane, 26 parts of dimethyldichlorosilane, and 445 parts of phenyltrichlorosilane was added dropwise over 50 minutes while stirring.

The reaction temperature rose once from 21°C to 600°C, and then fell to 35°C as hydrogen chloride gas was released.

The mixture was then gradually heated to 90° C. and further heated with stirring for 30 minutes to remove hydrogen chloride.

The concentration of hydrochloric acid in the alkoxysilane produced was 2.3.

After cooling to room temperature, 853 parts of toluene was added to obtain a toluene solution of organoalkoxysilane.

While stirring this, 366 parts of water was added dropwise over 30 minutes.

Refluxing, separation, dehydration, and solvent removal were carried out in the same manner as in Example 1 to obtain a solvent-free polyorganosiloxane resin.

For comparison, 628 parts of the same silane formulation as in Example was dissolved in 700 parts of toluene, and this was added to a mixed solution of 6,000 parts of water, 251 parts of Improper Tool, and 1130 parts of acetone at a reaction temperature of 40°C. The hydrolysis and condensation reactions were carried out by adding the mixture dropwise while adjusting the dropping rate so as to achieve the desired results.

The dropping time was 40 minutes.

The following steps of static separation, water washing, and solvent removal were carried out in the same manner as in the comparative example listed in Example 1 to obtain a polyorganosiloxane resin as a comparative sample.

When the molecular weight distribution of the obtained resin E was measured by gel permeation chromatography in the same manner as in Example 1, it was found that the molecular weight distribution of the comparative sample E was between 300 and 5000. Ri is 200-1000
It showed a smaller molecular weight distribution.

Furthermore, 25 parts each of resins D and E were added, and 50 parts of amorphous silica, 24 parts of glass fiber, and 0.25 parts of benzoic acid were added.
and 0.25 parts of lead carbonate and 0.5 parts of calcium stearate.
The components were mixed and kneaded uniformly using two rolls to obtain a molding composition.

These were molded at a temperature of 1165°C and an acid form pressure of 60 kg/a.
When transfer molding was carried out with a molding time of 3 minutes, the composition using the resin showed good flowability and curability, and a molded product was easily obtained.

On the other hand, the composition using resin E was insufficiently cured and a complete molded article could not be obtained.

Example 4 A reactor was charged with 830 parts of isopropanol, 240 parts of methyltrichlorosilane, and 19 parts of dimethyldichlorosilane.
4 parts of phenyltrichlorosilane and 423 parts of phenyltrichlorosilane were added dropwise over 50 minutes.

The reaction temperature was once raised from 21°C to 60°C, and then decreased to 35°C as hydrogen chloride gas was released.

The mixture was then gradually heated to 900C and heated for an additional 40 minutes with stirring to remove hydrogen chloride.

The concentration of hydrochloric acid in the alkoxysilane produced was 2.2%.

Next, the mixture was cooled to room temperature, and 850 parts of methylcyclohexane was added thereto to obtain a methylcyclohexane solution of organoalkoxysilane.

While stirring this, 380 parts of water was added dropwise over 30 minutes.

Refluxing, separation, dehydration, and concentration adjustment were carried out in the same manner as in Example 1 to obtain a 70f0 methylcyclohexane solution F of polyorganosiloxane resin.

For comparison, 70 parts of methylcyclohexane was added instead of 700 parts of toluene from a silane formulation having the same composition as in the example.
In the same manner as in the comparative example of Example 3 except that 0 part was used,
A 70% methylcyclohexane solution G of polyorganosiloxane resin was obtained.

Oil-free alkyd resin, Bellacolite M6401-
50 (product name of Nippon Reichhold) and melamine resin,
Knee pants 208E (product name of Mitsui Toatsusha) and resin 6:4
A coating obtained by adding a polyorganosiloxane resin solution as shown in Table 3 was applied to a steel plate, and 15
When the coating was cured by baking at 0° C12O, the results of the coating film were as shown in Table 3.

Example 5 740 parts of inbutanol was charged into a reactor, and a silane blend consisting of 475 parts of phenyltrichlorosilane and 125 parts of hexyltrichlorosilane was added dropwise over 35 minutes while stirring.

The reaction temperature rose once from 20°C to 60°C, and then dropped to 40'C with the release of hydrogen chloride gas.

The mixture was then gradually heated to 110° C. and heated for an additional 30 minutes with stirring to remove hydrogen chloride.

The mW of hydrochloric acid in the alkoxysilane produced was 1.8.

This was cooled to room temperature and 550 parts of xylene was added.
A xylene solution of alkoxysilane was obtained.

While stirring this, 320 parts of water was added dropwise over 30 minutes.

After the dropwise addition was completed, the temperature was raised to 90°C and refluxed with stirring for 30 minutes.

Then, heating and stirring were stopped, and the mixture was allowed to stand for 15 minutes to remove the acidic aqueous layer.

The concentration was adjusted in the same manner as in Example 1 to obtain a 70% xylene solution of polyorganosiloxane resin.

In order to examine the drying properties of this resin solution, gelation time was measured on a hot plate at 150° C. without the addition of a catalyst, and gelation occurred in 30 minutes.

In addition, in a 30φ xylene solution of polyorganosiloxane resin obtained by further adjusting the concentration of the resin solution of -A, the compatibility with epoxy resin Epicor 1-1001 (trade name of Shell Chemical Co., Ltd.) was investigated. It was confirmed that they were compatible in any proportion.

Example 6 A silane blend consisting of 225 parts of methyltrichlorosilane, 211 parts of phenyltrichlorosilane and 85 parts of silicon tetrachloride was charged into a reactor, and 450 parts of Impropasol and 64 parts of methanol were added dropwise over 40 minutes while stirring. did.

The reaction temperature rose once from 16"°C to 60°C, and then decreased to 40°C with the release of hydrogen chloride.

The mixture was then gradually heated to 70° C. and further heated with stirring for 40 minutes to remove hydrogen chloride.

The concentration of hydrochloric acid in the alkoxysilane produced was 2.6.

This was cooled to room temperature and 867 parts of 1-toluene was added to obtain a toluene solution of alkoxysilane.

While stirring, 550 parts of water was added dropwise over 45 minutes.

After the dropwise addition was completed, the temperature was raised to 80°C and refluxed with stirring for 30 minutes.

Next, heating and stirring were stopped, and the acidic aqueous layer was removed by standing for 10 minutes, followed by refluxing, separation, dehydration, and concentration adjustment in the same manner as in Example 1.
A 0% toluene solution was obtained.

In order to examine the drying properties of this resin solution, gelation time was measured on a 1500G hot plate in the absence of catalyst addition, and gelation occurred in 10 minutes.

For comparison, when the above silane formulation was hydrolyzed in the same manner as in the comparative example of Example 3, a large amount of fine gel substitute was produced.

[Brief explanation of drawings]

FIG. 1 shows the polymethylsiloxane resin A2 according to the present invention.
The results of measuring the molecular weight of comparative sample B2 using toluene as a standard solution are shown.

Claims (1)

[Claims] The average compositional formula selected from the group consisting of 11 types or 2 types of halosilanes and organonylosilanes is R1!
1SiX4-n (where R1 is a substituted or unsubstituted hydrocarbon group, X is a halogen atom, and n is a number from 0.5 to 1.7) as a starting material, single or mixed silanes In the method for producing a polyorganosiloxane resin, (a) the silane is mixed with the general formula R20H (wherein R2 is an alkyl group and 1 having 1 to 8 carbon atoms selected from alkyloxyethyl groups
(b) The resulting alkyl silicate and alkoxysilanes selected from the group consisting of organoalkoxysilanes are heated to a temperature above 70°C Ja to undergo halogenation. Continue heating until the remaining amount of hydrogen is 3 weight SJy or less, (c) add a water-insoluble organic solvent of 10 to 200% by weight of the alkoxysilanes, and (d) completely remove the alkoxysilanes. reacting with a sufficient stoichiometry of water for hydrolysis and condensation to form a polyorganosiloxane; (e) allowing the forming groups to stand and separating the acid-water mixture from the polyorganosiloxane layer; (f) ) by adding water and heating to a temperature of 60 to 100°C to remove the acid, then (g) removing the water and repeating steps (h) (f) and (g) as necessary. A method for producing a polyorganosiloxane resin, which comprises reducing the amount of hydrogen halide in the polyorganosiloxane resin to below 1 ppmJy. 2. The manufacturing method according to claim 1, wherein the halogen atom of the silane is a chlorine atom. 3. The manufacturing method according to claim 1, wherein R1 of the silane is a monovalent hydrocarbon group selected from a methyl group and a phenyl group. 4. The manufacturing method according to claim 1, wherein n of the silanes is a number of 1.0 to 1.3. 5. The manufacturing method according to claim 1, wherein the silane is organotrichlorosilane or a mixture of organotrichlorosilane and diorganodichlorosilane. 6. The manufacturing method according to claim 1, wherein the amount of alcohol added in step 6(a) is 1.0 to 1.2 mol per 1 mol of the halogen atom of the silane. 7) The manufacturing method according to claim 1, wherein in step 0, the heating temperature is 90 to 120°C. 8. The manufacturing method according to claim 1, wherein the amount of the water-insoluble organic solvent added in step 8(c) is 50 to 150% by weight of the alkoxysilane. 9. A method for producing a polyorganosiloxane resin, which comprises adding a step of removing alcohol and an organic solvent to the method described in claim 1.