JPS6256116B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a molded article for molten metal that has excellent corrosion resistance, heat resistance, and oxidation resistance.
More specifically, the present invention mainly produces SiC (amorphous, β-type, α-type, or a mixture thereof) by heating at least the external surface of a molded body made of ceramics to a temperature of 400 to 2000°C. This is a method for producing a molded body for molten metal with excellent corrosion resistance, heat resistance, and oxidation resistance, which comprises coating the coated molded body with a compound (hereinafter referred to as a semi-inorganic compound) that converts into ceramics consisting of a phase) and heat-treating the coated molded body. . The molded bodies produced by the method of the present invention are particularly suitable for phosphor bronze, pig iron, converter slag, blast furnace slag, metals (alkali metals, alkaline earth metals, transition metals,
It has excellent corrosion resistance against typical metals, semimetals, rare earth metals, actinium metals), alloys, their molten bodies, and metal molten salts. The method of the present invention will be explained in more detail below. In the first step of the method of the invention, at least the external surface of the shaped body to be treated is coated with at least one semi-inorganic compound (ie an organic-inorganic compound). Examples of the above-mentioned semi-inorganic compounds that can be used in the present invention include linear, cyclic, ladder-like, cage-like, three-dimensional or mesh-like compounds described in (1) to (11) below. can. (1) Polycarbosilane represented by the following formula (In the above formula, R ₁ to R ₅ are each hydrogen, a C ₄ or less alkyl group, a C ₄ or less haloalkyl group, a phenyl group, a C ₅ to C ₈ cycloalkyl group, a benzyl group, or a vinyl group; n is 10 to 10,000) (2) Polysilane represented by the following formula (In the above formula, R ₁ to R ₅ are each hydrogen, a C ₄ or less alkyl group, a C ₄ or less haloalkyl group, a phenyl group, a C ₅ to C ₈ cycloalkyl group, a benzyl group, or a vinyl group; n is 10 to 10,000) (3) Polycarbosiloxane represented by the following formula (In the above formula, R ₁ to R ₇ are each hydrogen, a C ₄ or less alkyl group, a C ₄ or less haloalkyl group, a phenyl group, a C ₅ to C ₈ cycloalkyl group, a benzyl group, or a vinyl group; n is 10 to 10,000; and includes both random and block repetitions of x units and y units) (4) Polycarbosiloxane represented by the following formula (In the above formula, R ₁ and R ₂ are each a C ₄ or less alkyl group, a C ₄ or less haloalkyl group, a phenyl group, a C ₅ to C ₈ cycloalkyl group, a benzyl group, or a vinyl group; R ₃ is Represents any one of the following to 〓, an alkenyl group of C ₆ or less (-(CH ₂ ) n-,
n≦6) Propylene group

[Formula] Vinylene group (-CH=CH-) Propenyl group (-CH ₂ -CH=CH-) Cyclopentylene group (-C ₅ H ₈ -) Cyclohexylene group (-C ₆ H ₁₀ -) Cyclohexenylene Group (−C ₆ H ₈ −) Alkenedicarbonyl group

【formula】 maloyl group

【formula】 Fumaroyl group (

【formula】 (Trance)) maleoyl group (

【formula】 (cis)) Phenylene group

【formula】 naphthylene group

[Formula] Anthrylene group

[Formula] Phenylenecarbonyl group

[Formula] Phenylene dicarbonyl group

【formula】 Phenicylene group

【formula】 glycerin group

【formula】 Diphenylene group

[Formula] X-bis(4-phenyl-) group

[Formula] [However, -X- is any one of the following
Representing the species, methane -CH ₂ - 2,2 propane

[Formula] Ether -O- Sulfide -S- Sulfoxide -SO- Sulfon -SO ₂ -] Benzene 1, 2, 4, 5 tetracarbonyl group

[Formula] Benzene 1, 2, 5 tricarbonyl group or benzene 1, 3, 5 tricarbonyl group

[Formula] 〓 〓 [However, -X- is -O-, -CH ₂ - or -S
-]; R ₄ is hydrogen, trimethylsilyl group, triphenylsilyl group, acetyl group or alkoxy group (<C ₄ )) (5) Polysiloxane represented by the following formula (In the above formula, R ₁ and R ₂ are each hydrogen, a C ₄ or less alkyl group, a C ₄ or less haloalkyl group, a phenyl group, a C ₅ to C ₈ cycloalkyl group, a benzyl group, or a vinyl group; R ₃ is hydrogen, a trimethylsilyl group, a triphenylsilyl group, an acetyl group, or an alkoxy group (<C ₄ ); n is 3≦n<10000 (6) A siloxane copolymer represented by the following formula (In the above formula, -X- is the formula

_[ Formula] represents _a siloxane having _a functionality _{of 5} to _C8 cycloalkyl group]; _R3 is hydrogen, a _C4 or less alkyl group, a _C4 or less haloalkyl group, a phenyl group, a _C5 to _C8 cycloalkyl group, a benzyl group or a vinyl group; 0≦k/l≦30 0≦m/k+l≦0.5 a=3~6 b=3~6 c=3~6 n<1000, and repetition of a, b, c units includes both random and block ) (7) Titanium-containing organosilicon polymer represented by the following formula (In the above formula, R ₁ , R ₂ and R ₄ are each a C ₄ or less alkyl group, a C ₄ or less haloalkyl group, a phenyl group, a C ₅ to _{C 8} cycloalkyl group, a benzyl group, or a vinyl group. ;R ₃ is a phenylene diamino group alkenediamino group (-NH( _-CH2 )-nNH-,
n≦6), hydrazo group (-NH-NH-), diphenylene 4,4' diamino or X-bis(phenyl4-amino [However, X is ether -O- methane -CH ₂
-, and R ₃ also includes a hydrochloride; n is 10 to 10,000) (8) A borosiloxane compound represented by the following formula (In the above formula, R ₁ to R ₃ are each hydrogen, a C ₄ or less alkyl group, a C ₄ or less haloalkyl group, a phenyl group, a C ₅ to _{C 8} cycloalkyl group, a benzyl group, or a vinyl group; (n is 1 to 10,000; and the repetition of the a unit and b unit includes both random and block) (9) The borosiloxane compound of the previous item (8), an aliphatic polyhydric alcohol, an aromatic alcohol, and a phenol. , or 1 selected from aromatic carboxylic acids
A modified borosiloxane compound obtained by reacting a species or two or more organic compounds at a temperature in the range of 250 to 450°C in an atmosphere inert to the reaction, optionally in the presence of a catalyst. (10) For the borosiloxane compound in the previous section (8),
Ni, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo,
Powder of at least one metal selected from W, Co and other transition metals, actenide metals and lanthanide metals and/or powder of alloys consisting of these metals, persulfates, organic peroxides, or Al Modified borosiloxane compound (11) obtained by adding at least one of the halides of Fe, B, Ga, and In as a catalyst and heating to 300 to 550°C in a non-oxidizing atmosphere (11) Previous item (9) A modified borosiloxane compound obtained by carrying out the reaction in (8) in the presence of any one or more of the catalysts used in (8). Regarding the method for producing the semi-inorganic compounds described in (1) to (11) above, the present inventors have previously filed an application for JP-A-51
-126300, JP-A-52-74000, JP-A-52-
112700, JP-A-53-42300, JP-A-54-028309,
Unexamined Japanese Patent Publications 1987-61298, 1983-61299, 1983-
No. 145642 and Japanese Patent Application Laid-Open No. 145643. Particularly preferred semi-inorganic compounds for use in the method of the present invention include, for example, the following: can be mentioned. In this case, the terminal group is a hydroxyl group, a methyl group, or a phenyl group. Preferred semi-inorganic compounds for use in the present invention are:
When converting into ceramics mainly composed of SiC (amorphous state, β-type, α-type, or a mixed phase of these) by heating to a temperature of 400 to 2000°C in a mainly non-oxidizing atmosphere, firing is performed. The residual rate is particularly high, ranging from 40 to 85%. Furthermore, not only can a highly concentrated solution be easily obtained, but it also has sufficient fluidity even at high concentrations, so the operation of coating the surface of the object to be treated with this solution can be carried out efficiently and easily. Can be done.
Since the adhesion between the object to be treated and the treatment solution is good, the coating obtained after heat treatment firmly adheres to the object to be treated, and has the advantage that it is less prone to cracking or peeling than the coating obtained by conventional methods. is obtained. The method of the present invention involves coating at least the outer surface (i.e., only the outer surface or both the outer surface and the inner surface) of a molded body made of ceramics with a semi-inorganic compound, and heat-treating the coated molded body thus obtained. As a result, the molded article is characterized by having excellent corrosion resistance, heat resistance, and oxidation resistance. Ceramics here means oxides, carbides, silicides, nitrides, borides, and boron. The molded bodies used in the method of the present invention are as follows (a)
Molded bodies as shown in ~(c) are included. (b) Commercially available ordinary molded bodies such as crucibles, bricks, cylinders, and tubes of Al ₂ O ₃ , MgO,
Such as SiC. (b) Commercially available inorganic molding material powder (Al ₂ O ₃ , MgO,
A molded body formed by sintering SiC) using the above-mentioned semi-inorganic compound used in the present invention as a binder. (c) By self-sintering the powder obtained by heating the semi-inorganic compound used in the present invention to 400 to 2000°C (preferably 500 to 1300°C) mainly in a non-oxidizing atmosphere, or A molded body obtained by sintering in combination with the above semi-inorganic compound. The method of the present invention, which comprises coating at least the external surface of the above molded body with a semi-inorganic compound and then heat-treating the coated molded body, includes various embodiments. In a first preferred embodiment of the method of the present invention, the surface of the heat-treated product having an arbitrary shape such as a plate, rod, fiber, or complex surface shape is coated with the semi-inorganic compound. This method heat-treats the coated material to form a corrosion-resistant, heat-resistant, oxidation-resistant protective film that firmly adheres to the surface of the workpiece. Particularly suitable workpieces to which this method is applied are, for example, metal melting crucibles made of ceramics such as alumina. Semi-inorganic compounds can be obtained as powders or viscous liquids, but in order to make the powders or viscous liquids coatable on objects to be treated, they can be mixed with solvents such as tetrahydrofuran, benzene, toluene, etc.
xylene, hexane, ether, dioxane, chloroform, methylene chloride, petroleum ether,
It is preferable to dissolve or dilute it in a solvent such as petroleum benzine, ligroin, chlorofluorocarbon, dimethyl sulfoxide, dimethyl formamide, etc., and use it as a coating solution. If it is obtained as a viscous liquid that can be coated, it can be used as is. The temperature of the heat treatment varies depending on the material of the object to be treated, but generally a heating temperature in the range of 400°C to 2000°C can be employed. As the heating atmosphere, it is preferable to use a non-oxidizing atmosphere (for example, an inert gas such as argon, nitrogen, hydrogen gas, CO gas, CO ₂ gas, or vacuum). In the case of siloxane (compounds (9), (10), and (11) in claims), air may be used. As a method for coating the surface of the object to be treated and heat-treating the coated object, various methods are possible and are not particularly limited, but for example, the following method can be used. (1) The surface of the object to be treated is coated with a coating solution by brushing or spraying, or the object is immersed in the coating solution and then pulled up to coat the surface, preferably using a non-oxidizing solution. A protective coating is formed by heating to a predetermined heat treatment temperature in a protective atmosphere. (2) Coating and heat treatment are performed simultaneously by spraying a coating solution onto the surface of the workpiece that has been heated to a predetermined heat treatment temperature, preferably in a non-oxidizing atmosphere. If desired, the coating and heat treatment may be repeated two or more times. A second preferred embodiment of the method of the invention uses a porous material (i.e. a material with an internal surface) as the object to be treated, and not only the external surface of the material, but also the internal surface. This is a method of forming a heat-resistant and oxidation-resistant protective coating that firmly adheres to both the external and internal surfaces of the material by applying a coating of a semi-inorganic compound and then heat-treating the coating. . Porous objects to be treated to which this method is applied are generally made of ceramics, such as high frequency conductors (susceptors) made of porous ceramics used to melt high melting point metals such as tungsten. can be cited as an example of a porous object. In this method, it is necessary to sufficiently coat not only the external surface but also the internal surface. Most preferred is the method of impregnating a part. Heat treatment is usually in a non-oxidizing atmosphere, with temperatures ranging from 400 to 2000
Preferably, the heating is carried out at a temperature of .degree. If desired, the impregnation step and heat treatment step may be performed more than once. A third preferred embodiment of the method of the present invention uses a powder material as the object to be treated, and after coating the surface of the powder with a semi-inorganic compound, the coated powder is molded by a suitable method known per se, for example. Forming a molded product into a desired shape by a molding method such as a mold press method, a rubber press method, an extrusion method, a sheet method, etc.
This is a method for producing a heat-resistant and oxidation-resistant material by heat-treating this material. In this embodiment, the coating of a semi-inorganic compound applied to the surface of the powder serves as a binding material when obtaining a molded body from the powder, and thereby the powder is firmly bonded to each other and heat-resistant. At the same time, the coating layer formed on the externally exposed surface of the molded product provides the molded product with corrosion resistance, heat resistance, and oxidation resistance. Helpful. In the above method, the method for coating the surface of the powder is to sufficiently mix the viscous liquid of the semi-inorganic compound and the powder of the material to be treated, or the method of sufficiently mixing the viscous liquid of the semi-inorganic compound and the powder of the material to be treated. and,
A method of thoroughly mixing in the presence of a solvent as described above, or a method of immersing the powder of the object to be treated in a solution containing a semi-inorganic compound and then taking it out can be adopted. The thus obtained powder of the object to be treated, whose surface is coated with a semi-inorganic compound, is made into a molded body by an appropriate molding method, and the molded body is heat-treated, but the heat treatment is performed after molding. Alternatively, it may be performed simultaneously with molding. Heat treatment is usually performed in a non-oxidizing atmosphere at a temperature of 400 to
Preferably, this is carried out by heating to a temperature within the range of 2000°C. The above method of producing a corrosion-resistant, heat-resistant, oxidation-resistant material by surface coating, molding, and heat treatment on a powdered object is a method suitably applied to ceramic powder. be. A fourth preferred embodiment of the method of the present invention is to prepare the semi-inorganic compound in a primarily non-oxidizing atmosphere.
The above-mentioned semi-inorganic compound is applied to a molded body obtained by self-sintering the powder obtained by heating it to 400-2000°C (preferably 500-1300°C) or by sintering it in combination with the above-mentioned semi-inorganic compound. The inorganic compound is coated (externally and internally) and then heat treated.
The coating method and heat treatment conditions are as described in Embodiment 1 to
According to 3. The molded bodies obtained by the method of the present invention are particularly suitable for phosphor bronze, pig iron, converter slag, blast furnace slag, metals (alkali metals, alkaline earth metals, transition metals,
It has excellent corrosion resistance against typical metals, semimetals, rare earth metals, actinium metals), alloys, their melts, and metal molten salts, as well as heat resistance and oxidation resistance. In molded bodies obtained by conventional methods, such as the pitch impregnation method, the coated and impregnated fired product is made of carbon, so oxidative consumption is severe especially under conditions of use in air, and corrosion resistance against the above-mentioned molten body, as well as oxidation resistance and heat resistance. There are also limits in terms of. On the other hand, the molded product obtained by the present invention is chemically stable because its surface and internal pores are filled with SiC, and exhibits excellent corrosion resistance and oxidation resistance. Furthermore, since the expansion coefficient of the SiC is small, the molded product has excellent heat resistance, such as improved thermal shock resistance. The molded product obtained by the present invention is characterized by extremely excellent corrosion resistance against melts as described above, but it is also superior to conventional molded products under other general conditions (e.g., heating conditions in air). It is excellent. The present invention will be explained below with reference to Examples. Example 1 2.5 g of anhydrous xylene and 383 g of sodium were placed in the 5-necked flask, and 1 portion of dimethyldichlorosilane was added dropwise little by little under an argon gas stream. After the dropwise addition was completed, the mixture was similarly heated under reflux for 8 hours in an argon stream to form a precipitate. This precipitate was thoroughly washed with methanol and then with water to obtain polysilane as a white powder. This polysilane was placed in an autoclave and reacted at 450°C for 20 hours. After the reaction was completed, it was dissolved in n-hexane, taken out from the autoclave, filtered, and heated and concentrated to 100°C using a vacuum pump to obtain a solid semi-inorganic compound (polycarbosilane). After melting and coating the above semi-inorganic compound on various types of commercially available ceramic crucibles for melting metals,
The molded article of the present invention was obtained by heating to 1300°C. Converter slag and blast furnace slag were placed in a crucible and heated to 1600°C, and the time taken for the molten material to seep into the crucible shell was measured, and the results were as follows.

[Table] As an example, the attached drawing shows a comparison between an untreated crucible and a treated crucible regarding the corrosion resistance of a SiC crucible filled with converter slag and held at 1600°C for one day. In the accompanying drawing, the outer peripheral surface of the untreated crucible subjected to the above test cut in half lengthwise is shown on the right side, and leaching of the contents is observed. The right side is the outer circumferential surface of the crucible that has been coated twice and heat treated.
It can be seen that the corrosion resistance is improved. Other ceramics such as Al ₂ O ₃ -SiO ₂ , Si ₃ N ₄
A similar coating effect was observed for the crucible,
Especially phosphor bronze, pig iron, converter slag, blast furnace slag,
For molten metals and molten metal carbonates, an extension of service life of 2 to 5 times that of untreated crucibles was observed. Example 2 The polysilane obtained during the semi-inorganic compound synthesis of Example 1 was mixed with commercially available MgO, Al ₂ O ₃ , Al ₂ O ₃ −
It was placed in an autoclave together with SiO ₂ , SiC, and Si ₃ N ₄ ceramic crucibles, held at 450°C for 20 hours, and then taken out and heated in nitrogen to 1300°C to obtain a molded article of the present invention. The corrosion resistance, oxidation resistance, and heat resistance of each ceramic crucible obtained were equivalent to those of the molded product obtained in Example 1. Example 3 253 g of dichlorodiphenylsilane and 62 g of ethylene glycol were dissolved in 500 ml of n-butyl ether and heated at 90 to 100°C while refluxing for 24 hours.
The reaction continued for hours. After completion of reaction, under reduced pressure of 20mmHg
The solvent and unreacted substances were distilled off at 200°C. The obtained semi-inorganic compound (polycarbosiloxane) was melt-coated on a commercially available plate-shaped SiC (purity 99%, density 2.8 g/cm ³ ) and then heated to 1700°C in nitrogen (coating and heating twice). A molded article of the present invention was obtained. The molded body was immersed in molten pig iron and phosphor bronze at 1300°C for 20 hours, then pickled with dilute nitric acid, and the corrosion loss was measured. In the case of molten pig iron, the corrosion weight loss of the treated molded body was 1/4 that of the untreated molded body. Similarly, in the case of fused phosphor bronze, it was 1/3. Similar coating effects have been observed for other ceramic plates (Al ₂ O ₃ , Al ₂ O ₃ -SiO ₂ , MgO, Si ₃ N ₄ , etc.), especially phosphor bronze, pig iron, converter slag, and blast furnace slag. For molten metal and molten metal carbonate, the corrosion loss of the treated plate was less than 1/3 of that of the untreated plate. Example 4 15 parts by weight of the semi-inorganic compound used in Example 1 was added to 99.9% pure SiC powder with an average of 600 meshes, mixed thoroughly, and then press-molded into a crucible shape and heated in nitrogen at room temperature.
It was fired to 1300℃ for 8 hours to form a SiC crucible. This crucible was melt-coated with the semi-inorganic compound used in Example 2, and then heated to 1700° C. (repeated twice) to obtain a molded article of the present invention. The weight loss due to immersion corrosion for molten pig iron and molten phosphor bronze was 1/3 to 1/4 that of untreated molded bodies under the same conditions, which was a good result. Example 5 253 g of dichlorodiphenylsilane and 110 g of p-hydroquinone were dissolved in 500 ml of THF solvent.
The reaction was continued for 24 hours while heating and refluxing at 100°C. After the reaction was completed, the solvent was removed. The product obtained was a viscous solid. The number average molecular weight determined by the VPO measurement method was 3000. Phenoxy-diphenylsiloxane polymer obtained as described above was melt-coated onto a commercially available SSA-H alumina crucible and heated to 1700°C in argon. The thus obtained molded product of the present invention was immersed in molten pig iron and phosphor bronze at 1300° C. for 20 hours, and the corrosion loss was measured, and the result was 1/3 of that of the untreated molded product. Example 6 310g of boric acid and 1898 diphenyldichlorosilane
g was put into a three-necked flask (No. 5) together with 3 n-butyl ether, and reacted at 100° C. with stirring for 18 hours. After cooling, a white precipitate was obtained. After removing n-butyl ether, the precipitate was washed with methanol to remove unreacted boric acid, and then washed with water to obtain 1680 g of a borodiphenylsiloxane compound. 200 g of this borodiphenylsiloxane compound, 20 g of hydroquinone and 1 g of ammonium persulfate were mixed homogeneously in a 500 ml flask, heated at a temperature increase rate of 50°C for 1 hour in a nitrogen atmosphere with stirring, and then heated to 300°C for 1 hour. The mixture was reacted for a period of time to obtain a pale yellow semi-inorganic compound. After mixing 5 parts by weight of this semi-inorganic compound and 1 part by weight of borosilicate glass in powder form, the mixture was placed in a carbon die and heated at high frequency (hot press) to 1000°C under a pressure of 100 kg/cm ² . The obtained molded body was heated to 500℃10
It has excellent oxidation resistance, with no weight change even when heated in air for hours, and is suitable for heating elements and resistors used at temperatures below 1300℃. Example 7 Put anhydrous xylene 2 and 300 g of metallic sodium into the three-necked flask from Step 5, heat it to the boiling point of xylene (136°C) in a nitrogen gas stream, and add 540 g of dimethyldichlorosilane and diphenyldichlorosilane.
460 g of the mixture was added dropwise from the dropping funnel 1 at a rate of 0.3/hour. After the dropwise addition was completed, heating was continued for 18 hours to produce a blue-purple precipitate. This precipitate is filtered and washed first with methanol and then with water to form a white powder of polymethylphenylsilane.
Obtained 470g. This semi-inorganic compound is commercially available as SSA.
-H Alumina crucible was fused and coated at 1700 °C in argon.
Heated to ℃. The thus obtained molded product of the present invention was immersed in molten pig iron and phosphor bronze at 1300°C for 20 hours, and the corrosion loss was measured.
It was 1/4 warm. Example 8 102g of glycerin and dichlorodiphenylsilane
Dissolve 365g in 500ml of n-butyl ether and make 90~
The reaction was carried out for 18 hours while heating and refluxing at 100°C. The product was dissolved in benzene to remove unreacted glycerin, and the solvent was distilled off to obtain a semi-inorganic compound. The obtained semi-inorganic compound (polycarbosiloxalane) was melt coated on a commercially available SiC plate (purity 99%, density 2.8 g/cm ³ ) and then heated at 1700°C in nitrogen.
The molded article of the present invention was obtained by heating (coating and heating twice). The molded body was immersed in molten pig iron and phosphor bronze at 1300°C for 200 hours, then pickled with dilute nitric acid and the corrosion loss was measured. In the case of molten pig iron, the corrosion weight loss of the treated molded body was 1/5 of that of the untreated molded body. Similarly, in the case of fused phosphor bronze, it was 1/4. Other ceramic plates (Al ₂ O ₃ , Al ₂ O ₃ −
_A similar coating effect was observed for phosphor _bronze , pig iron, converter slag, blast furnace slag, molten metal, molten metal carbonate, _etc. ). The corrosion loss of the treated board remained at less than 1/4 of that of the untreated board.

[Brief explanation of the drawing]

The accompanying drawings are diagrams showing the difference in corrosion resistance between the untreated crucible (right side) and the treated crucible (left side) described in Example 1.

Claims (1)

[Claims] 1. By heating at least the outer surface of a molded body made of ceramics to a temperature of 400 to 2000°C, SiC (amorphous state, β type, α type, or a mixed phase thereof) can be formed. A method for producing a molded body for molten metal with excellent corrosion resistance, heat resistance, and oxidation resistance, which comprises coating the coated molded body with a compound that converts into ceramics consisting of the following, and heat-treating the coated molded body. 2 The above-mentioned compound to be converted into ceramics mainly consisting of SiC (amorphous state, β type, α type, or a mixed phase thereof) has a linear, cyclic, ladder-like, cage-like, three-dimensional or mesh-like shape. Below (1)
The manufacturing method according to claim 1, characterized in that it is at least one of the compounds described in (11). (1) Polycarbosilane represented by the following formula (In the above formula, R ₁ to R ₅ are each hydrogen, a C ₄ or less alkyl group, a C ₄ or less haloalkyl group, a phenyl group, a C ₅ to C ₈ cycloalkyl group, a benzyl group, or a vinyl group; n is 10 to 10,000) (2) Polysilane represented by the following formula (In the above formula, R ₁ to R ₅ are each hydrogen, a C ₄ or less alkyl group, a C ₄ or less haloalkyl group, a phenyl group, a C ₅ to C ₈ cycloalkyl group, a benzyl group, or a vinyl group; n is 10 to 10,000) (3) Polycarbosiloxane represented by the following formula (In the above formula, R ₁ to R ₇ are each hydrogen, a C ₄ or less alkyl group, a C ₄ or less haloalkyl group, a phenyl group, a C ₅ to _{C 8} cycloalkyl group, a benzyl group, or a vinyl group; n is 10 to 10,000; and the repetition of x units and y units includes both random and block) (4) Polycarbosiloxane represented by the following formula (In the above formula, R ₁ and R ₂ are each a C ₄ or less alkyl group, a C ₄ or less haloalkyl group, a phenyl group, a C ₅ to _{C 8} cycloalkyl group, a benzyl group, or a vinyl group; R ₃ represents any one of the following to 〓, and C ₆ or less alkenyl group (-(CH ₂ ) n-,
n≦6) Propylene group [Formula] Vinylene group (-CH=CH-) Propenyl group (-CH ₂ -CH=CH-) Cyclopentylene group (-C ₅ H ₈ -) Cyclohexylene group (-C ₆ H ₁₀ −) Cyclohexenylene group (-C ₆ H ₈ −) Alkenedicarbonyl group [Formula] Maloyl group [Formula] Fumaroyl group ([Formula] (trans)) Maleoyl group ([Formula] (cis)) Phenylene group [ Formula] Naphthylene group [Formula] Anthrylene group [Formula] Phenylenecarbonyl group [Formula] Phenylene dicarbonyl group [Formula] Phenysylene group [Formula] Glycerin group [Formula] Diphenylene group [Formula] X-bis(4-phenyl- ) group [Formula] [However, -X- is any one of the following
Methane -CH ₂ - 2,2 Propane [Formula] Ether -O- Sulfide -S- Sulfoxide -SO- Sulfon -SO ₂ -] Benzene 1, 2, 4, 5 Tetracarbonyl group [Formula] Benzene 1・2.5 tricarbonyl group or benzene 1.3.5 tricarbonyl group [Formula] 〓 〓 [However, -X- is -O-, -CH ₂ - or -S
-]; R ₄ is hydrogen, trimethylsilyl group, triphenylsilyl group, acetyl group or alkoxy group (<C ₄ )) (5) Polysiloxane represented by the following formula (In the above formula, R ₁ and R ₂ are each hydrogen, a C ₄ or less alkyl group, a C ₄ or less haloalkyl group, a phenyl group, a C ₅ to C ₈ cycloalkyl group, a benzyl group, or a vinyl group; R ₃ is hydrogen, a trimethylsilyl group, a triphenylsilyl group, an acetyl group, or an alkoxy group (<C ₄ ); n is 3≦n<10000 (6) A siloxane copolymer represented by the following formula (In _the above formula, _-X- represents a siloxane having _the functionality of formula _R3 is hydrogen, _an alkyl _group of up to _C4 , a haloalkyl group of _up to _C4 , a phenyl group, a _C5 - _C8 cyclo Alkyl group, benzyl group or vinyl group; 0≦k/l≦30 0≦m/k+l≦0.5 a=3-6 b=3-6 c=3-6 n<1000, and a, b, c Unit repeats include both random and block repeats) (7) Ni-containing organosilicon polymer represented by the following formula (In the above formula, R ₁ , R ₂ and R ₄ are each a C ₄ or less alkyl group, a C ₄ or less haloalkyl group, a phenyl group, a C ₅ to C ₈ cycloalkyl group, a benzyl group, or a vinyl group. ;R ₃ is a phenylene diamino group alkenediamino group (-NH( _-CH2 )-nNH-,
n≦6), hydrazo group (-NH-NH-), diphenylene 4,4' diamino or X-bis(phenyl4-amino [However, X is ether -O- methane -CH ₂
-, and R ₃ also includes a hydrochloride; n is 10 to 10,000) (8) A borosiloxane compound represented by the following formula (In the above formula, R ₁ to R ₃ are each hydrogen, a C ₄ or less alkyl group, a C ₄ or less haloalkyl group, a phenyl group, a C ₅ to C ₈ cycloalkyl group, a benzyl group, or a vinyl group; n is 1 to 10,000; and the repetition of the a unit and b unit includes both random and block) (9) The borosiloxane compound of the previous item (8), an aliphatic polyhydric alcohol, an aromatic alcohol, a phenol, or 1 selected from aromatic carboxylic acids
A modified borosiloxane compound obtained by reacting a species or two or more organic compounds at a temperature in the range of 250 to 450°C in an atmosphere inert to the reaction, optionally in the presence of a catalyst. (10) For the borosiloxane compound in the previous section (8),
Ni, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo,
Powder of at least one metal selected from W, Co and other transition metals, actenide metals and lanthanide metals and/or powder of alloys consisting of these metals, persulfates, organic peroxides, or Al Modified borosiloxane compound (11) obtained by adding at least one of the halides of Fe, B, Ga, and In as a catalyst and heating to 300 to 550°C in a non-oxidizing atmosphere (11) Previous item (9) A modified borosiloxane compound obtained by carrying out the reaction in (8) in the presence of any one or more of the catalysts used in (8).