JPS63117037A - Organosilazane polymer and production of ceramics therefrom - Google Patents

Abstract

PURPOSE:To facilitate the formation of the title polymer which is excellent in heat resistance and moldability and can give a ceramic molding excellent in strength and elastic modulus, by polymerizing an ammonolysis product obtained by reacting methyldichlorosilane, methyltrichlorosilane and a specified organosilicon compound with ammonia. CONSTITUTION:A mixture of 55-90mol% methyldichlorosilane (A) with 5-30mol% methyltrichlorosilane (B) and an organosilicon compound (C) of the formula (wherein R1 is Cl, Br, CH3, C2H5 or phenyl, R2 is H or R1, R3-4 are each H or CH3 and X is Cl or Br) is reacted with NH3 to give an ammonolysis product. This product is polymerized at 0-200 deg.C in the presence of a deprotonating basic catalyst (D) such as an alkali (alkaline earth) metal hydride or a metal amide (e.g., KH or NaNH2) in a solvent (E) such as tetrahydrofuran, hexane or toluene, and the remaining catalyst is decomposed with, e.g., methyl iodide. The formed insoluble matter is filtered off and the solvent is distilled off from the mixture to give the title polymer of an intrinsic viscosity of 0.06-0.09.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an organic silazane polymer suitably used as a ceramic precursor, and a method for producing ceramics using the organic silazane polymer.

The sun is about to grow □ Although ceramics are attracting attention as materials with excellent heat resistance, abrasion resistance, and high-temperature strength, they are hard.

And because of their brittleness, it is extremely difficult to process ceramics. Therefore, when manufacturing ceramic products, it is necessary to form fine powder of ceramic material into a desired shape by applying pressure or other methods and then sintering it, or by melting or dissolving an organic polymer as a ceramic precursor in a solvent. However, a precursor method is adopted in which the material is processed into a desired shape and then fired to make it inorganic. The most important feature of the precursor method is that it is possible to obtain ceramic products in shapes that are impossible with the sintering method using fine powder, and therefore it is possible to produce products in special shapes such as fibers or sheets.

In this case, among what is generally called ceramics, S
iC, Si, and N4 are attracting wide attention because they have excellent properties at high temperatures, with SiC having excellent heat resistance and high-temperature strength, and Si and N having excellent thermal shock resistance and fracture toughness. For this reason, various proposals have been made in the past regarding methods for producing 5iC-8i3N based ceramics and methods for producing organosilicon precursors thereof using precursor methods, as shown in (1) to (3) below. All of them had problems. That is, (2) U.S. Pat. No. 3,853,567 discloses that chlorosilanes and amines are reacted, and then
After heating to 0°C to obtain carbosilazane, this is spun,
A method for obtaining 5iC-SilN4 ceramics by making it infusible and firing at a high temperature of 800 to 2000°C is disclosed. However, this method requires a high temperature of 520 to 650°C to obtain carbosilazane, which is extremely difficult as an industrial production method, and the ceramic yield is about 55% when mineralizing carbosilazane. The disadvantage is that the yield is low. In addition, in the examples of this US patent specification, the chlorosilanes include methyltrichlorosilane, dimethyldichlorosilane,
As for amines, only methylamine is mentioned.

■U.S. Pat. No. 4,097,294 shows that various silicon-containing polymers can be converted into ceramic materials by pyrolysis.

However, only one example of a silazane polymer has been disclosed, and the ceramicization yield thereof is as low as 12% at maximum. Furthermore, although this US patent specification states that it is possible to make ceramics into fibers and thin films, this is merely a suggestion of that possibility.
There is no mention of polymer moldability and processability, which are most important in precursor methods.

■Unexamined Japanese Patent Publication No. 57-117532 discloses that the reaction between chlorodisilanes and disilazane
No. 9124 discloses the reaction between chlorosilanes and disilazanes, and JP-A-58-63725 discloses the reaction between chlorodisilanes and ammonia.
Publication No. 135431 discloses that silazane polymers can be obtained by reacting trichlorosilane and disilazane. Also, U.S. Patent No. 4,535,00
In the specification of No. 7, by adding metal halides to chlorosilanes and disilazane, JP-A-60-20
Publication No. 8331 discloses that silazane polymers are produced by adding metal halides to chlorodisilanes and disilazanes. All of the silazane polymers of 0 or more can be made into ceramics by thermal decomposition. It is said that there is. However, the ceramization yield was 50-60 for any silazane polymer.
%, which is a low yield. In addition, the above-mentioned publications do not describe in detail the moldability and processability of polymers, which are the most important in the precursor method, as in the specification (2), and in particular, the publications without examples of fiberization Or, even if there are examples of fiberized fibers, most do not mention the strength of the ceramicized fibers. Slightly JP-A-60-20
The description of strength can be found in Publication No. 8331, but in this case as well, the tensile strength is 53 kg/m2 or 63 kg/m2.
Only extremely low strength specimens, ie, "m", have been obtained.

A method is disclosed in which an ammonolysis product is obtained by the reaction of the organosilicon compound represented by the formula with ammonia, and then this product is subjected to dehydrogenation condensation with an alkali metal or alkaline earth metal hydride to obtain a silazane polymer. There is. It is said that the properties of the polymer obtained by this method can be varied depending on the degree of dehydrogenation condensation, from oil-like to solid with no melting point. However, when molding and processing a polymer from a molten state, for example when producing continuous fibers by melt spinning, it is necessary that the polymer has a certain degree of polymerization and is thermally stable. If the polymerization is not stopped midway, the polymer will become a solid with no melting point, and in order to obtain a meltable polymer, delicate control of reaction time, reaction temperature, amount of catalyst, amount of solvent, etc. is required. There are problems in that adjustment is extremely difficult and reproducibility is lacking.

Furthermore, the polymer obtained by this method has the disadvantage that it is not thermally stable and is accompanied by the formation of a gel-like substance.From one or more of these points, the above method is suitable for producing a cyclic silazane from a compound represented by silazane and monomethylamine. A method is shown in which a silazane polymer is obtained by forming a cyclic silazane and reacting this cyclic silazane with ammonia. but,
Although the above publication states that the polymer is suitable as a material for chemical vapor deposition, there is no detailed description of the physical properties of the polymer, nor is there any mention of ceramic yield.

As mentioned above, polysilazane polymers that have been proposed in the past as ceramic precursors are unsuitable for industrial production, have poor formability and processability as precursors for ceramic fibers, etc., and have poor ceramic yield. The rate was low. Furthermore, ceramic products 1 such as ceramic fibers manufactured using conventional polysilazane polymers as precursors are inferior in various physical properties such as strength and elastic modulus.

The present invention was made in view of the above circumstances, and includes a method for producing a ceramic precursor that is suitable for industrial production, has excellent moldability and workability, and has a high ceramic yield, and a high-quality ceramic precursor using the ceramic precursor. The purpose of the present invention is to provide a method for manufacturing ceramics.

. In order to do so, the present inventors have developed a method for manufacturing a ceramic product that belongs to the precursor method, and a method for manufacturing a ceramic precursor that is suitable for manufacturing this ceramic product and has excellent industrial efficiency and workability. To develop.

Focusing on 5iC-8i, N4-based ceramics, which have the excellent high-temperature properties of SiC, Si, and N4, we conducted intensive research on a method for manufacturing 5iC-3i, N, based ceramics using a precursor method, and found that methyldichlorosilane , methyltrichlorosilane, the following general formula (1) (However, R1 is chlorine, bromine, methyl group, ethyl group, or phenyl group, R2 is hydrogen, chlorine, bromine, methyl group, ethyl group, or phenyl group, R□ and R4 is hydrogen or a methyl group,
Three types of chlorosilanes of organosilicon compounds represented by X represent chlorine or bromine, respectively) are mixed and reacted with ammonia to obtain an ammonolysis product. By carrying out dehydrogenation condensation using a catalyst capable of deprotonation such as a hydride or metal amide, and completing this condensation reaction, a polysilazane polymer with excellent thermal stability and a constant degree of polymerization can be obtained. Furthermore, it was discovered that high-quality ceramics mainly composed of SiC, Si, and N4 could be obtained by melting and molding this droplet polysilazane polymer, making it infusible by heating in air or irradiating it with electron beams, and firing it. However, the present invention has been completed.

Therefore, 1 the present invention provides an ammonolysis product by reacting a mixture of methyldichlorosilane, methyltrichlorosilane, and an organosilicon compound represented by the above formula (1) with ammonia, and also deprotonates this ammonolysis product. Provided is a method for producing an organic silazane polymer, characterized in that the organic silazane polymer is obtained by polymerization using a basic catalyst.

Furthermore, the present invention provides an ammonolysis product obtained by reacting a mixture of methyldichlorosilane, methyltrichlorosilane, and an organosilicon compound of formula (1) with ammonia, and a base capable of deprotonating the ammonolysis product. To provide a method for producing ceramics, which comprises: first obtaining an organic silazane polymer by polymerizing with a chemical catalyst, then melting and molding the organic silazane polymer, making it infusible, and then firing it to obtain ceramics.

The method for producing an organosilazane polymer according to the present invention uses three types of starting materials: methyldichlorosilane, methyltrichlorosilane, and the organosilicon compound of formula (1), and allows a mixture of these to react with ammonia. After
An organic silazane polymer with excellent thermal stability and a constant degree of polymerization can be obtained simply by applying a catalyst to the product and completing the dehydrogenation condensation. Therefore, according to the method of the present invention, a high-quality organic silazane polymer with excellent moldability and processability and a high ceramic yield (usually 70 to 80%) can be produced using a reaction time, a reaction temperature, a catalyst amount, a solvent amount, etc. It can be easily produced industrially without requiring delicate control or troublesome operations such as stopping the polymerization midway.

Furthermore, the present inventors had previously proposed a method for producing an organic silazane polymer using a three-component system of methyldichlorosilane, dimethyldichlorosilane, and methyltrichlorosilane (Japanese Patent Application No. 135437/1983); Compared to the method
Since the present invention uses the organosilicon compound of formula (1) above as a starting material, it has a wide range of possible compositions and is industrially advantageous.

Further, there is a method for manufacturing ceramics according to the present invention.

By using the above-described organic silazane polymer as a precursor, it is possible to easily produce a ceramic product having an appropriate shape and having excellent physical properties.

As mentioned above, it has been known to use chlorosilanes as raw materials for producing silazane polymers, which are ceramic precursors. However, by selecting the three types of chlorosilanes mentioned above, ammonolyzing them, and then catalyzing the product to complete the dehydrogenation, a silazane polymer with unprecedented properties has been created. It is a new finding of the present inventors that this can be obtained. That is, methyldichlorosilane, methyltrichlorosilane, and the organosilicon compound of formula (1) are used in combination, and preferably these are
By using 90 mol%: 5 to 30 mol% = 2 to 30 mol%, methyldichlorosilane as described in JP-A No. 60-226890 etc. can be used alone. It is possible to obtain a new silazane polymer having a structure different from that of the conventional silazane polymer, in which various repeating units and bond structures of these repeating units are mixed, and what is the structure of such conventional silazane polymers. By using a silazane polymer with a new and different structure as a ceramic precursor, the yield of ceramics is greatly improved compared to the conventional method of manufacturing ceramics using this type of precursor method, and the yield of ceramics is improved, such as tensile strength and modulus of elasticity. The present inventors have discovered for the first time that ceramics with significantly improved physical properties can be produced.

The present invention will be explained in more detail below.

In the method for producing an organosilazane polymer according to the present invention, methyldichlorosilane, methyltrichlorosilane, and the organosilicon compound represented by the above formula (1) are used in combination as starting materials. In this case, the combination ratio is 55
~90 mol%: 5 to 30 mol% = 2 to 30 mol% is suitable; if the composition ratio is outside this range, the obtained polymer may become oily or have a high melting point (3
00°C or higher).

The present invention also provides an ammonolysis product by reacting the mixture of the chlorosilanes with ammonia. In this case, there is no limitation on the method of reacting ammonia, but for example, a method such as reacting the above mixture with gaseous NH3 in an organic solvent, removing by-produced ammonium chloride, and then stripping the organic solvent is preferable. Adopted.

Next, in one aspect of the present invention, the above-mentioned ammonolysis product is polymerized using a basic catalyst capable of deprotonation. In this case, during deprotonation, it is preferable to dehydrogenate the ammonorinse product in a solvent with a catalyst to complete the reaction. Here, the basic catalyst capable of deprotonation is K Hv N a
Hydrides or metal amides of alkali metals or alkaline earth metals such as Hp Na N Hz vKNH, etc. can be suitably used. Examples of solvents that can be used in one polymerization step include ethers such as THF and dialkyl ethers, and aliphatic hydrocarbons such as pentane and hexane.

One or more aromatic hydrocarbons such as benzene, toluene, and xylene can be used. Incidentally, one polymerization can be carried out at room temperature, but depending on the type of solvent, the polymerization temperature can be appropriately selected in the range of 0 to 200°C.

Furthermore, in the method of the present invention, after completing the dehydrogenation condensation reaction, the remaining basic catalyst species are decomposed with an electrophilic compound such as methyl iodide, and the generated insoluble matter is removed by passing; Furthermore, it is preferable to distill off the solvent under reduced pressure.
9(7) polysilazane polymer can be obtained. In this case, completion of the condensation reaction can be confirmed by stopping the gas generated.

The degree of polymerization and melting point of the silazane polymer can be adjusted as appropriate by changing the blending ratio of chlorosilanes.

The organic silazane polymer obtained in this way can be formed into an appropriate shape, especially a fiber or sheet shape, as a ceramic precursor, as shown in the following, by taking advantage of its high moldability and processability. Although preferred, use as a binder or adhesive is also possible.

The method for producing ceramics according to the present invention involves melting and shaping the above-mentioned organic silazane polymer, making it infusible, and then firing it. In this case, it is preferable to use a polymer having a melting point of 60 to 200 DEG C. and an intrinsic viscosity of 0.06 to 0.09 as the main body polymer, which allows the polymer to be easily melted and molded.

Furthermore, there are no particular limitations on the methods of melting, shaping and firing the organic silazane polymer, and ceramic products of various shapes can be obtained by shaping the polymer into an appropriate shape and firing it.

For example, when producing ceramic fibers, an organic silazane polymer can be first melted by heating and then spun using a melt spinning method. In this case, the spinning temperature in this step varies depending on the melting point of the polymer, but it is usually preferably carried out in the range of 100 to 300°C.First, the filament obtained in this spinning step is heated in air or , in vacuum or N
It is made infusible by electron beam irradiation in a gas, inert gas, etc. In this step, heating in air is preferably carried out at a temperature of 50 to 150°C, and electron beam irradiation is preferably carried out at a dose of 50 to 200 Mrad.

By firing the infusible filament at high temperature under no tension or under tension, it is possible to obtain ceramic fibers mainly composed of Sxc e S 13 N4 and having excellent strength and elastic modulus. In this process, firing is performed in vacuum or in
Inert gas such as r, N2 gas, N2 gas.

70 in one or more gases such as NH, gas, etc.
It is preferable to carry out the reaction at a temperature of 0 to 2000°C, particularly 700 to 1500°C. In this case, it is particularly preferable to fire under tension, which results in a tensile strength of 200 to 300 kg/
2. High quality ceramic fibers with physical properties of elastic modulus of 15 to 30 t/1rys can be produced.

Furthermore, as explained above, according to the method for producing an organic silazane polymer according to the present invention, it is thermally stable and has a certain degree of polymerization, and therefore has excellent moldability and processability, and is also suitable for use in ceramics. The organic silazane polymer, which has a high yield and can therefore be particularly suitably used as a precursor for ceramic fibers, can be industrially advantageously produced.

Furthermore, according to the method for manufacturing ceramics according to the present invention,
High-quality ceramics mainly composed of SiC, Si, and N can be obtained with a high ceramic yield. in this case,
According to the method of the present invention, ceramic products of a desired shape, such as ceramic fibers, ceramic sheets, etc., can be successfully produced, and as a result, ceramic fibers with excellent strength and elastic modulus,
You can get sheets etc.

Furthermore, the present invention has the advantage that by using the organosilicon compound of formula (1) as a starting material, the range of possible compositions thereof is wide.

EXAMPLES The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples below.

〔Example〕

Ammonolysis [Methyldichlorosilane: Methyltrichlorosilane: 1
, 2-bis(methyldichlorosilyl)ethane = 75:1
0:15 (mol%)] Equipped with a stirrer, thermometer, NH, inlet tube, and deep-cooled condenser, add 850 mol of hexane to a dry IQ four-loaf flask.
After charging aQ, methyldichlorosilane 43,1
g eAdd 7.5 g of methyltrichlorosilane and 19.2 g of 1,2-bis(methyldichlorosilyl)ethane,
Cooled to -20°C. Excess gaseous ammonia to 450
/Hr for 1.5 hours (NH, total addition 3.0 mol).

The reaction mixture was warmed to room temperature, while the condenser was replaced with an air-cooled condenser to allow unreacted NH, to escape. Next, by-product ammonium chloride was removed from the reaction mixture in a dry box by passing it through.

The cake was further washed with 200-hexane, and the hexane was stripped from the P solution under reduced pressure (60° C., 71 m+8 g). The residue (ammonolysis product) was a clear fluid liquid, 31 g was obtained.

Ammonolysis ■ [Methyldichlorosilane: Methyltrichlorosilane: 1
, 2-bis(methyldichlorosilyl)ethane = 65:2
5:10 (mol %)] 850 mR of hexane was charged into an IQ 4-bottle flask equipped with the same equipment as above, and 3 ml of methyldichlorosilane was added to this.
7.4gt Methyltrichlorosilane 18.6g, 1,
2-bis(methyldichlorosilyl)ethane 12.8 g
was added and cooled to -20'C.

Gaseous ammonia was added to this solution at a rate of 451/Hr for 1.5 hours. Thereafter, 30g of clear fluid liquid (ammonolysis product) was treated in the same manner as above.
I got it.

Ammonolysis ■ [Methyldichlorosilane: Methyltrichlorosilane = 1
, 2-bis(trichlorosilyl)ethane = 75:15:
10 (mol%)] Put 1500 mQ of dehydrated hexane into a 2Q four-bottle flask equipped with the same equipment as above, and add methyldichlorosilane s.
9, Og v methyltrichlorosilane 17.9 g
, 1,2-bis(trichlorosilyl)ethane 23.8
g was added thereto and reacted with gaseous ammonia in the same manner. Thereafter, it was treated in the same manner as in (1) above to obtain 48 g of a transparent fluid liquid (ammonolysis product).

A 300 mL three-bottle flask was equipped with a stirrer, a thermometer, and a dropping funnel, and T was dehydrated with 0.2 g (5 mmol) of potassium hydride and NaH in a dry box.
HF125d was injected into the flask.

This flask was taken out of the dry box and connected to a nitrogen pipe. At room temperature, while stirring the mixture to disperse KH, the product Log obtained in the ammonolysis step (2) dissolved in THF75- was slowly added over 15 minutes from the dropping funnel. A large amount of gas evolution was observed during this addition, and the gas evolution stopped after 1 hour. When 3 g of methyl iodide was added, a white precipitate of KI formed. After stirring for an additional 30 minutes, most of the THF solvent was removed under reduced pressure and 80 d of hexane was added to the remaining white slurry.

This mixture was passed through, and the P solution was removed under reduced pressure (1 mdg) at 70°C.
When hexane was removed, 9.1 g of viscous solid (silazane polymer) was obtained.

This product had an intrinsic viscosity (benzene, 20°C) of 0.06, a melting point of 90°C, and was soluble in hexane, benzene, THF, and other organic solvents. Also, 3400 from IR
NH on Bei-1, 298 km "C-H on 1.

2150 (5L-H in 1m-1, 5L-H in 1260a1-1
iCH.

Absorption of each of these was observed. Further, the molecular weight was determined to be 820 by the benzene freezing point depression method.

The ammonolysis product Log obtained in the ammonolysis step ⑰ was mixed with 0.2 g of KH in THF in the same manner as in the polymerization step ②.
It was allowed to react for 0 minutes. After gas generation stopped, CH and I were added,
The same process was performed below.

9.3 g of a viscous solid (silazane polymer) was obtained, which had an intrinsic viscosity of 0.08. The melting point was 120"C.

The ammonolysis product Log obtained in the heavy"
It was allowed to react for 0 minutes. After gas generation stopped, CH and I were added,
The same process was performed below.

9.1 g of a viscous solid (silazane polymer) was obtained, which had an intrinsic viscosity of 0.07. The melting point was 115°C.

30 g of the silazane polymer obtained in the polymerization step (1) was melt-spun at 130° C. using a monohole spinning device. Spinning is 4
Very good even after hours, winding speed 400 m/+++i
The raw silk obtained was further heated to 120 M with an electron beam.
Infusibility treatment was performed using rad. Then, under slight tension, at a heating rate of 100'C/Hr in a N2 stream,
It was baked at 0°C for 30 minutes. The ceramic yield was 75%, and the obtained fibers had a fiber diameter of 6μ and a tensile strength of 230kg.
/w+”.

The physical property was an elastic modulus of 22t/m''.Furthermore, when the fiber composition was analyzed by elemental analysis, it was found that 5L was 58.6%;
5iC consisting of C19.0%, N 20.4%, 02%
It was confirmed that the fibers were mainly composed of -8L and N4.

The silazane polymer Log obtained in the polymerization step (2) was melt-spun at 160° C. using the same spinning device as in the fiberization step (2). The winding speed was 420 m/min, and the spinning was very good. Furthermore, the obtained raw silk was heated at 90 to 110°C (5°C/Hr) in air under slight tension to make it infusible.
It was baked at 1200° C. for 30 minutes at a temperature increase rate of 100 hr. The ceramic yield was 80%, and the obtained fibers had a fiber diameter of 8.
μ, tensile strength 200kg/l1m”, elastic modulus 17t/m
”, elemental analysis of the fiber composition revealed that it was 5155
．． 6%, C17.8%, N 17.4%, 09.2%
The fiber was mainly composed of 5iC-8i□N.

2. Silazane polymer obtained in 2. was melt-spun in a dry box at 150° C. and at a winding speed of 450 m/win using the same spinning device as in the fiberization step ①. The spinning was good from beginning to end. The obtained raw silk was irradiated with 90 Mrad using an electron beam device in a vacuum to make it infusible. Thereafter, the obtained fibers were placed under tension in a N3 stream for 12
It was baked at 50°C (100°C/Hr) for 30 minutes. Ceramic yield was 77%. In addition, the fiber diameter is 6μ
The tensile strength was 250 kg/Kaku 81 and the elastic modulus was 23 t/■2.

[Comparative example]

After 850 d of dehydrated hexane was charged into a 1Ω four-bottle flask equipped with an ammonium sieve stirrer, a thermometer, NH, an inlet tube, and a deep-cooled condenser, 46 g of methyldichlorosilane was added. Gaseous ammonia was introduced into the mixture at a rate of 12 Q/hr for 3.5 hours to cause one reaction. Thereafter, the same treatment as in the ammonolysis step (2) of the above example was carried out to obtain 20 g (85%) of a transparent fluid liquid.

KHo, 2g and THF in 3 300id flasks
After injecting L 25-, KH was dispersed by stirring, and a mixture of THF75d and the previously obtained transparent fluid liquid Log was added dropwise from the dropping funnel over 15 minutes at room temperature. 30 minutes after the completion of the 0 drop addition. to stop the reaction midway through CH,I
Added 2g. Hereinafter, the same treatment as in the polymerization step (2) of one example was performed.

9.0 g of a viscous solid was obtained. The intrinsic viscosity of this material is 0.0
B. The melting point was 75°C.

An attempt was made to control the temperature, amount of catalyst, and polymerization time to maintain a constant degree of polymerization in this system, but the results lacked reproducibility.

8g of the obtained silazane polymer was poured into a monohole (nozzle 0
, 5 amφ) was charged into a spinning device, melted at 110° C., and spun. At first, the discharge from the nozzle was good,
Although spinning was possible, the nozzle stopped discharging after 30 minutes. Although the temperature was gradually raised, the polymer did not discharge at all. After cooling, the polymer was taken out and its melting point was measured. It was found that it did not melt even at 300° C. and was also insoluble in the solvent. After irradiating the slightly spun raw silk with an electron beam at 90 Mrad, N
It was fired at 1100°C for 30 minutes in two air streams at a heating rate of 100°C/Hr. The ceramic yield was 58%, and the obtained fibers had a fiber diameter of 7 μm and a tensile strength of 50 kg/mum.
The physical properties were low, with an elastic modulus of 5 t/am.

Claims (1)

[Claims] 1. Methyldichlorosilane, methyltrichlorosilane and the following general formula (1) ▲There are numerical formulas, chemical formulas, tables, etc.▼・・・・・・(1) (However, R_1 is chlorine, bromine, Methyl group, ethyl group or phenyl group, R_2 is hydrogen, chlorine, bromine, methyl group,
Ethyl group or phenyl group, R_3 and R_4 represent hydrogen or methyl group, and X represents chlorine or bromine, respectively. ) is reacted with ammonia to obtain an ammonolysis product, and this ammonolysis product is polymerized with a basic catalyst capable of deprotonation to obtain an organosilazane polymer. A method for producing an organic silazane polymer. 2. The mixing ratio of methyldichlorosilane, methyltrichlorosilane, and the organosilicon compound represented by the general formula (1) is 55 to 90 mol%: 5 to 30 mol%: 2 to 30 mol%
The manufacturing method according to claim 1. 3. The manufacturing method according to claim 1 or 2, wherein the organosilicon compound of formula (1) is 1,2-bis(chlorodimethylsilyl)ethane. 4. The manufacturing method according to claim 1 or 2, wherein the organosilicon compound of formula (1) is 1,2-bis(dichloromethylsilyl)ethane. 5. The manufacturing method according to claim 1 or 2, wherein the organosilicon compound of formula (1) is 1,2-bis(trichlorosilyl)ethane. 6. The manufacturing method according to any one of claims 1 to 5, using KH, NaH, NaNH_2, or KNH_2 as the basic catalyst. 7. A mixture of methyldichlorosilane, methyltrichlorosilane, and the organosilicon compound of formula (1) is reacted with ammonia to obtain an ammonolysis product, and this ammonolysis product is polymerized using a basic catalyst capable of deprotonation. A method for producing ceramics, which comprises: obtaining an organic silazane polymer, then melting and shaping the organic silazane polymer, making it infusible, and then firing it to obtain ceramics. 8. Claim 7, wherein the mixing ratio of methyldichlorosilane, methyltrichlorosilane, and the organosilicon compound of formula (1) is 55 to 90 mol%: 5 to 30 mol%: 2 to 30 mol%. manufacturing method. 9. The manufacturing method according to claim 7 or 8, wherein the organic silazane polymer has a melting point of 60 to 200°C. 10. The production according to any one of claims 7 to 9, wherein the organic silazane polymer is melted and molded, and then heated in air to 50 to 150°C to make it infusible. Method. 11. After the organic silazane polymer is melted and molded, it is irradiated with an electron beam at a dose of 50 to 200 Mrad in vacuum or N_2 gas to make it infusible.Claims 7 to 9 The manufacturing method according to any one of the above. 12. The manufacturing method according to any one of claims 7 to 11, wherein the forming step is a spinning step, and the ceramic fiber is obtained by spinning a molten organic silazane polymer. 13. The manufacturing method according to any one of claims 7 to 12, wherein the firing temperature is 700 to 2000°C. 14. The manufacturing method according to any one of claims 7 to 13, wherein the firing atmosphere is in a vacuum or in a gas selected from inert gas, N_2 gas, H_2 gas, and NH_3 gas.