JPH0219135B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a method for producing an organic silazane polymer suitably used as a ceramic precursor. Problems to be solved by conventional techniques and inventions Ceramics are attracting attention as materials with excellent heat resistance, wear resistance, high temperature strength, etc. However, it is extremely difficult to process ceramics because they are hard and brittle. It is. Therefore, when manufacturing ceramic products, there are two methods: first forming a fine powder of ceramic material into a desired shape using a method such as pressurization, and then sintering it, or melting an organic polymer as a ceramic precursor or using a solvent. A precursor method has been adopted in which the material is melted, processed into a desired shape, and then fired to become inorganic. The most important feature of the above precursor method is that it is possible to obtain ceramic products in shapes that are impossible with the sintering method using fine powder, and it is therefore possible to produce products with special shapes such as fibers or sheets. be. In this case, SiC and Si ₃ N ₄ , which are generally called ceramics, are heat resistant and SiC, respectively.
It has attracted wide attention due to its excellent properties at high temperatures, such as excellent high-temperature strength, and Si ₃ N ₄ has excellent thermal shock resistance and fracture toughness. SiC by physical method
Various proposals have been made regarding methods for producing Si ₃ N ₄ ceramics and methods for producing organosilicon precursors thereof, but all of these proposals have had problems. That is, U.S. Pat. No. 3,853,567 discloses that chlorosilanes and amines are reacted, and then 200-
A method is disclosed in which SiC-Si ₃ N ₄ ceramics are obtained by heating to 800°C to obtain carbosilazane, spinning it, making it infusible, and firing at a high temperature of 800 to 2000°C. However, this method requires 520-650℃ to obtain carbosilazane.
This method requires high temperatures, making it extremely difficult as an industrial production method, and has drawbacks such as a low ceramic yield of about 55% when mineralizing carbosilazane. In addition, in the examples of this US patent specification, only methyltrichlorosilane and dimethyldichlorosilane are described as chlorosilanes, and methylamine is described as an amine. U.S. Pat. No. 4,097,294 shows that various silicon-containing polymers are converted into ceramic materials by pyrolysis. However, only one example of silazane polymers has been disclosed, and the yield of ceramic formation is as low as 12% at maximum. Additionally, although this US patent specifies that it is possible to make ceramics into fibers and thin films, this is merely a suggestion of that possibility, and it is not intended to be a mere suggestion of the possibility of making ceramics into fibers or thin films. There is no mention of moldability or processability. JP-A No. 57-117532 discloses that the reaction between chlorodisilanes and disilazane
-139124 describes the reaction between chlorosilanes and disilazane, JP-A-58-63725 describes the reaction between chlorodisilanes and ammonia, and JP-A-60-135431 describes the reaction between trichlorosilane and disilazane. It has been shown that silazane polymers can be obtained by reaction with each of the following. In addition, U.S. Patent No. 4,535,007 discloses that by adding metal halides to chlorosilanes and disilazane,
The publication discloses the production of silazane polymers by adding metal halides to chlorodisilanes and disilazanes, respectively. It is said that all of the above silazane polymers can be made into ceramics by thermal decomposition. However, the ceramicization yield for all silazane polymers is 50 to 60%, which is a low yield. In addition, each of the above publications is
Similar to the specification, the moldability and processability of the polymer, which are most important in the precursor method, are not described in detail, and in particular, there are no examples of fiberization or examples of fiberization. However, most of them do not mention the strength of the ceramic fibers. Slightly JP-A-60-208331
There is a description of strength in the publication, but in this case too, only extremely low tensile strength of 53 Kg/mm ² or 63 Kg/mm ² was obtained. In Japanese Patent Application Laid-Open No. 60-226890,

A method of obtaining an ammonolysis product by the reaction of an organosilicon compound represented by the formula with ammonia, and then dehydrogenating the product with an alkali metal or alkaline earth metal hydride to obtain a silazane polymer. Disclosed. It is said that the properties of the polymer obtained by this method can be varied from oil-like to solid with no melting point depending on the degree of dehydrogenation condensation. 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 constant degree of polymerization and is thermally stable.
In the above method, if the polymerization is not stopped midway, the polymer becomes 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. However, there are problems in that it is very difficult to adjust and lacks reproducibility. Furthermore, the polymer obtained by this method has disadvantages such as not being thermally stable and accompanied by the formation of gel-like substances.For these two reasons, the above method is not suitable as an industrial method for producing silazane polymers. do not have. In Japanese Patent Application Laid-Open No. 60-228489,

〔Example〕

Ammonolysis step [Methyldichlorosilane: Methyltrichlorosilane: 1,2-bis(methyldichlorosilyl)
Ethane = 75:10:15 (mol%)] Equipped with a stirrer, a thermometer, an NH ₃ inlet tube, and a deep-cooled condenser, 850 ml of hexane was charged into a dry four-necked flask, and then 43.1 ml of methyldichlorosilane was added. g, methyltrichlorosilane 7.5g, 1,
2-bis(methyldichlorosilyl)ethane 19.2g
was added and cooled to -20°C. Excess gaseous ammonia was added to this solution at a rate of 45/Hr for 1.5 hours (total addition of NH ₃ 3.0 mol). The reaction mixture was warmed to room temperature while the condenser was replaced with an air-cooled condenser to allow unreacted _NH3 to escape. Next, by-produced ammonium chloride was removed from the reaction mixture in a dry box by filtration. 200ml more cake
Wash with hexane and remove from the liquid under reduced pressure (60℃/1
mmHg). The residue (ammonolysis product) was a clear flowable liquid, yielding 31 g. Ammonolysis step [Methyldichlorosilane: Methyltrichlorosilane: 1,2-bis(methyldichlorosilyl)
Ethane = 65:25:10 (mol%)] Pour 850 ml of hexane into a four-necked flask (1) equipped with the same equipment as above, add 37.4 g of methyldichlorosilane, 18.6 g of methyltrichlorosilane,
1,2-bis(methyldichlorosilyl)ethane
12.8g was added and cooled to -20°C. Gaseous ammonia was added to this solution at a rate of 45/Hr for 1.5 hours. Thereafter, the same treatment as above was carried out to obtain 30 g of a transparent fluid liquid (ammonolysis product). Ammonolysis step [Methyldichlorosilane: Methyltrichlorosilane: 1,2-bis(trichlorosilyl)ethane = 75:15:10 (mol%)] 1500 ml of dehydrated hexane was added to 2 four-necked flasks equipped with the same equipment as above. Add 69.0g of methyldichlorosilane, 17.9g of methyltrichlorosilane, 1.
23.8 g of 2-bis(trichlorosilyl)ethane was added and reacted with gaseous ammonia in the same manner. It was then treated in the same manner as above to obtain 48 g of a clear fluid liquid (ammonolysis product). Polymerization Step A 300 ml three-necked flask was equipped with a stirrer, a thermometer, and a dropping funnel, and 0.2 g (5 mmol) of potassium hydride and 125 ml of THF dehydrated with NaH were poured into the flask in a dry box. 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, add 10 g of the product obtained in the ammonolysis step dissolved in 75 ml of THF from the dropping funnel.
Added slowly over 15 minutes. A large amount of gas evolution was observed during this addition, and the gas evolution stopped after 1 hour. Addition of 3 g of methyl iodide produced a white precipitate of KI. After stirring for an additional 30 minutes, most of the
The THF solvent was removed under reduced pressure and 80 ml of hexane was added to the remaining white slurry. The mixture was filtered and the hexane was removed from the liquid under reduced pressure (1 mmHg) at 70°C to obtain 9.1 g of a viscous solid (silazane polymer). This product has an intrinsic viscosity (benzene, 20℃) of 0.06,
It had a melting point of 90°C and was soluble in hexane, benzene, THF and other organic solvents. Also, from IR, 3400cm ^-1 NH, 2980cm ^-1 C-H, 2150cm ^-1
Absorption of Si-H at 1260 cm ^{-1 and} SiCH ₃ at 1260 cm -1 were observed. Furthermore, the molecular weight was determined to be 820 by benzene freezing point depression method. Polymerization process 10g of the ammonolysis product obtained in the ammonolysis process was added to THF in the same manner as in the polymerization process.
The reaction was carried out with 0.2 g of KH for 90 minutes. After gas generation stops
CH ₃ I was added and the same treatment was carried out. 9.3 g of a viscous solid (silazane polymer) was obtained, which had an intrinsic viscosity of 0.08 and a melting point of 120°C. Polymerization process 10g of the ammonolysis product obtained in the ammonolysis process was added to THF in the same manner as in the polymerization process.
The reaction was carried out with 0.2 g of KH for 90 minutes. After gas generation stops
CH ₃ I was added and the same treatment was carried out. 9.1 g of a viscous solid (silazane polymer) was obtained, which had an intrinsic viscosity of 0.07 and a melting point of 115°C. In addition, methyldichlorosilane (MDCS), methyltrichlorosilane (MTCS), and 1,2-bis(methyldichlorosilyl)ethane (BMDCSE)
Table 1 shows the results of ammonolysis and polymerization in the same manner as above with different molar ratios. Here, No. in Table 1 corresponds to the polymer obtained in the above-mentioned ammonolysis step, polymerization step, etc., respectively.

[Reference example]

Fiberization process 30g of the silazane polymer obtained in the polymerization process was spun into 130 g by a monohole spinning device (nozzle diameter 0.5mm).
Melt spinning was carried out at ℃. The spinning was very good even after 4 hours, and it was carried out at a winding speed of 400 m/min, and the obtained raw silk was further infusible treated with an electron beam at 120 Mrad. Then under slight tension and in a _N2 stream
It was baked at 1100°C for 30 minutes at a heating rate of 100°C/Hr. The ceramic yield was 75%, and the obtained fibers had a fiber diameter of 6μ, a tensile strength of 230Kg/mm ² , and an elastic modulus of 22t/mm ²
It was a physical property. In addition, when the fiber composition was analyzed by elemental analysis, Si 58.6%, C 19.0%,
It was confirmed that the fiber was mainly composed of SiC-Si ₃ N ₄ containing 20.4% N and 2% O. Fiberization step 10 g of the silazane polymer obtained in the polymerization step was melt-spun at 160° C. using the same spinning device as in the fiberization step. The winding speed was 420 m/min, and the spinning was very good. Furthermore, the obtained raw silk was heated at 90 to 110℃ (5℃/Hr) in air under slight tension.
It was heated to make it infusible. Then under no tension
At 1200°C with a heating rate of 100°C/Hr in a _N2 stream
Bake for 30 minutes. The ceramic yield is 80%,
The obtained fiber has a fiber diameter of 8μ, a tensile strength of 200Kg/mm ² ,
The elastic modulus was 17t/ ^mm2 . Elemental analysis of the fiber composition revealed that Si 55.6%, C 17.8%, N 17.4%,
The fiber was mainly composed of SiC-Si ₃ N ₄ containing 9.2% O. Fiberization step 20 g of the silazane polymer obtained in the polymerization step was melt-spun in a dry box at 150° C. at a winding speed of 450 m/min using the same spinning device as in the fiberization step. 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 fired for 30 minutes at 1250° C. (100° C./Hr) in a N ₂ stream under tension. The ceramic yield was 77%. The fibers had a fiber diameter of 6μ, a tensile strength of 250Kg/mm ² , and an elastic modulus of 23t/mm ² . Note that Table 2 shows the results when the silazane polymers shown in Table 1 were melt-spun.

[Comparative example]

Ammonolysis process After charging 850 ml of dehydrated hexane into a four-necked flask equipped with a stirrer, thermometer, NH ₃ inlet tube, and deep-cooled condenser, methyl dichlorosilane was added.
Added 46g. Add 12% gaseous ammonia to this
hr rate for 3.5 hours and allowed to react. below,
A treatment similar to the ammonolysis step of the above example was carried out to obtain 20 g (85%) of a clear flowable liquid. Polymerization process KH0.2g and THF125 in a 300ml three-necked flask
ml was injected, the KH was dispersed by stirring, and a mixture of 75 ml of THF and 10 g of the previously obtained transparent fluid liquid was added dropwise from the dropping funnel over 15 minutes at room temperature.
To stop the reaction 30 minutes after completion of the dropwise addition.
12g of _CH3 was added. Thereafter, the same treatment as in the polymerization step of the example was carried out to obtain 9.0 g of a viscous solid. This product had an intrinsic viscosity of 0.06 and a melting point of 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 this resulted in a complete lack of reproducibility. Fiberization Step 8 g of the obtained silazane polymer was charged into a monohole (nozzle 0.5 mmφ) spinning device, melted at 110° C., and spun. Initially, the nozzle discharged well and spinning was possible, but after 30 minutes the nozzle no longer discharged. 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, and 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, it was heated at 100°C/Hr in a _N2 stream.
It was baked at 1100°C for 30 minutes at a heating rate of . The ceramic yield was 58%, and the obtained fibers had a fiber diameter of
It had low physical properties, with a tensile strength of 50 Kg/mm ² and an elastic modulus of 5 t/mm ² . Tables 3 and 4 show the results obtained when the same operations as in this comparative example were carried out under various conditions.

【table】

[Table] As shown in Tables 3 and 4, Polymer No. 7
Since Polymer No. 7 did not melt even at 300°C and melt spinning was impossible, Polymer No. 7 was dissolved in toluene and dry spun. However, yarn breakage was severe and continuous spinning was not possible, and although the small amount of fiber obtained was fired, the physical properties after firing were a fiber diameter of approximately 15μ and a tensile strength of 42
Kg/mm ² and tensile modulus of elasticity was only 5t/mm ² . Therefore, in order to obtain a polymer with a melting point of 300°C or less, various polymers were produced by changing reaction conditions.
For example, in a polymerization process, when the reaction time or gas generation amount reaches a certain stage, the reaction mixture is
An attempt was made to stop the reaction by adding CH ₃ I. Although a polymer with a relatively low melting point was obtained by this method, the reproducibility was very poor. In addition, melt spinning was performed on low melting point polymers No. 16, 17, and 18, but the nozzles stopped spinning immediately after the polymers melted, and the residue remaining in the melt spinning device was cooled and the melting point was measured again. As a result, it no longer melted even at 300°C. Therefore, in the method of this comparative example, in order to obtain a polymer that can be melt-spun, the reaction must be stopped during polymerization, and the reproducibility of the obtained polymer is poor (if polymerization is performed under the same conditions). However, it was found that the obtained polymer lacked stability in melt spinning, making continuous spinning difficult. On the other hand, as is clear from the results in Tables 1 and 2, by using methyldichlorosilane, dimethyldichlorosilane, and the compound of formula (1) in combination, continuous melting at a low melting point can be achieved. It has been found that a silazane polymer is obtained which can be spun. In this case, when the two components were used in combination (No. 5 and No. 6) lacking the compound of formula (1), the obtained silazane polymer could not be melt-spun continuously for a long period of time.

Claims (1)

[Claims] 1. Methyldichlorosilane, methyltrilorosilane and the following general formula (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
represents hydrogen or a 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
The manufacturing method according to claim 1, wherein the amount is mol%. 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. Claim 1, wherein the organosilicon compound of formula (1) is 1,2-bis(trichlorosilyl)ethane.
The manufacturing method described in item 1 or 2. 6 KH, NaH, NaNH ₂ or
The manufacturing method according to any one of claims 1 to 5, using KNH ₂ .