JPH0827276A - Silicon-containing combustionproof material - Google Patents

Abstract

PURPOSE:To obtain the subject material, light in weight, excellent in processability, having high heat resistance, and generating no toxic gas or smoke when combusted, useful for automotive parts, etc., containing a silicon- contg. high-molecular compound having specific bonds in its recurring unit. CONSTITUTION:This material contains a silicon-contg. high-molecular compound (or a cured product thereof) having each at least one Si-H bond and CidenticalC bond in its recurring unit. It is preferable that the compound has a structure expressed by formula I, II or III (R<1>-R<3> are each H, a 1-30C alkyl, alkenyl, alkynyl, or an aromatic group such as phenyl or naphthyl; R<4> is a 1-30C alkylene, alkenyl, alkynylene, or a divalent aromatic group such as phenylene or naphthyl) and 500-1000000 in weight-average molecular weight.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a combustion resistant material characterized by containing silicon in its structure.

[0002]

2. Description of the Related Art For buildings and materials used for them, fire resistance depending on the use, structure and scale of the building,
Fire resistance is required. The development of materials that do not cause harmful flame spread, deformation, heat transmission, smoke generation, and generation of harmful gas in the event of fire has been advanced. In recent years, these requirements have been increasing due to the increase in the number of buildings. In addition, parts around engines of automobiles and aircraft, materials for space,
It is desired to develop materials that are lightweight and have excellent heat resistance and combustion resistance, such as electronic parts.

For this reason, a method is generally adopted in which a flame retardant containing phosphorus, halogen or other inorganic elements or inorganic salts is mixed with an industrial resin such as polyurethane, unsaturated polyester resin, epoxy resin, polyolefin or polystyrene. Has been done. Thermosetting resins such as phenol resin, urea resin, melamine resin, and silicon resin, and resins such as polyimide, polyvinylidene chloride, and polytetrafluoroethylene have relatively high combustion resistance. However, the flame resistance of these resins is not sufficient, and there are many problems such as generation of harmful halogen gas with polyvinylidene chloride, polytetrafluoroethylene, etc., which have high flame resistance.

[0004]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The inventors of the present invention have made diligent efforts to develop a material that is lightweight, has excellent workability, has high heat resistance, and does not generate harmful gas or smoke during combustion. The inventors have found that a silicon-containing material having a certain structure satisfies these conditions, and have reached the present invention.

[0005]

The present invention comprises a silicon-containing polymer compound having at least one Si-H bond and a C≡C bond in a repeating unit, or a cured product of the silicon-containing polymer compound. Combustion resistant material.

The silicon-containing polymer compound in the present invention has at least one Si--H bond and one C≡C bond in a repeating unit, and the repeating portion is at least one polymer. / 3 or more. For example, structural formula (1) (chemical formula 4)

[0007]

[Chemical 4] (In the formula, R ¹ is hydrogen or an aromatic group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkynyl group, a phenyl group and a naphthyl group, and these are halogen,
It may contain a substituent such as a hydroxyl group, an amino group or a carboxyl group. ), Structural formula (2) (chemical formula 5)

[0008]

Embedded image (In the formula, R ² is hydrogen or an aromatic group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkynyl group, a phenyl group and a naphthyl group, and these are halogen,
It may contain a substituent such as a hydroxyl group, an amino group or a carboxyl group. ) Or structural formula (3) (Chemical formula 6)

[0009]

[Chemical 6] (In the formula, R ³ is hydrogen or an aromatic group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkynyl group, a phenyl group and a naphthyl group, and R ⁴ is an alkylene group having 1 to 30 carbon atoms. , An alkenylene group, an alkynylene group, a phenylene group, a naphthylene group, or another divalent aromatic group, which may contain a substituent such as a halogen, a hydroxyl group, an amino group, or a carboxyl group.). It is something. Specifically, structural formula (4) (Chemical formula 7)

[0010]

[Chemical 7] , Structural formula (5) (chemical formula 8)

[0011]

Embedded image , Structural formula (6) (chemical formula 9)

[0012]

[Chemical 9] , Structural formula (7) (chemical formula 10)

[0013]

[Chemical 10] , Structural formula (8) (chemical formula 11)

[0014]

[Chemical 11] , Structural formula (9) (chemical formula 12)

[0015]

[Chemical 12] , Structural formula (10) (chemical formula 13)

[0016]

[Chemical 13] , Structural formula (11) (Chemical formula 14)

[0017]

Embedded image , Structural formula (12) (chemical formula 15)

[0018]

[Chemical 15] , Structural formula (13) (chemical formula 16)

[0019]

Embedded image Structural formula (14) (Chemical formula 17)

[0020]

[Chemical 17] , Structural formula (15)

[0021]

Embedded image , Structural formula (16) (chemical formula 19)

[0022]

[Chemical 19] , Structural formula (17) (chemical formula 20)

[0023]

Embedded image , Structural formula (18) (chemical formula 21)

[0024]

[Chemical 21] , Structural formula (19) (chemical formula 22)

[0025]

[Chemical formula 22] Structural formula (20) (Chemical formula 23)

[0026]

[Chemical formula 23] , Structural formula (21)

[0027]

[Chemical formula 24] , Structural formula (22)

[0028]

[Chemical 25] Structural formula (23) (Chemical formula 26)

[0029]

[Chemical formula 26] Structural formula (24) (Chemical formula 27)

[0030]

[Chemical 27] , Structural formula (25) (chemical formula 28)

[0031]

[Chemical 28] , Structural formula (26) (chemical formula 29)

[0032]

[Chemical 29] Structural formula (27) (Chemical formula 30)

[0033]

Embedded image , Structural formula (28) (Chemical formula 31)

[0034]

[Chemical 31] , Structural formula (29) (chemical formula 32)

[0035]

Embedded image , Structural formula (30) (Chemical Formula 33)

[0036]

[Chemical 33] , Structural formula (31) (chemical formula 34)

[0037]

Embedded image , Structural formula (32) (chemical formula 35)

[0038]

Embedded image , Structural formula (33) (chemical formula 36)

[0039]

Embedded image , Structural formula (34) (Chemical Formula 37)

[0040]

Embedded image , Structural formula (35)

[0041]

[Chemical 38] , Structural formula (36) (Chemical formula 39)

[0042]

[Chemical Formula 39] , Structural formula (37) (Chemical formula 40)

[0043]

[Chemical 40] , Structural formula (38) (chemical formula 41)

[0044]

Embedded image Structural formula (39) (Chemical formula 42)

[0045]

Embedded image , Structural formula (40) (Chemical formula 43)

[0046]

[Chemical 43] , Structural formula (41)

[0047]

[Chemical 44] , Structural formula (42)

[0048]

Embedded image , Structural formula (43) (Chemical formula 46)

[0049]

Embedded image , Structural formula (44)

[0050]

[Chemical 47] , Or structural formula (45)

[0051]

Embedded image And so on. The weight average molecular weight is not particularly limited, but is preferably 500 to 1,000,000, more preferably 50.
It is 0-500000. The form is liquid or solid. These silicon-containing polymer compounds are preferably used alone, but can also be used together with other various polymer compounds.

The method for producing these silicon-containing polymer compounds has been proposed by the present inventors (Japanese Patent Application No. 5-43).
596, Japanese Patent Application No. 5-179709, Japanese Patent Application No. 5-2230
09, Japanese Patent Application No. 5-236445, Japanese Patent Application No. 6-4231
0, Japanese Patent Application No. 6-6791), for example, reaction formula (46)
(Chemical 49)

[0053]

[Chemical 49] (In the formula, R ¹ is hydrogen or an aromatic group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkynyl group, a phenyl group and a naphthyl group, and these are halogen,
It may contain a substituent such as a hydroxyl group, an amino group or a carboxyl group. ), Reaction formula (47)

[0054]

Embedded image (In the formula, R ² is hydrogen or an aromatic group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkynyl group, a phenyl group and a naphthyl group, and these are halogen,
It may contain a substituent such as a hydroxyl group, an amino group or a carboxyl group. ), Reaction formula (48) (Chemical formula 51)

[0055]

[Chemical 51] (In the formula, R ³ is hydrogen or an aromatic group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkynyl group, a phenyl group and a naphthyl group, and R ⁴ is an alkylene group having 1 to 30 carbon atoms. A divalent aromatic group such as an alkenylene group, an alkynylene group, a phenylene group or a naphthylene group, which may contain a substituent such as a halogen, a hydroxyl group, an amino group or a carboxyl group) or a reaction formula. (49) (Chemical 52)

[0056]

Embedded image (In the formula, R ³ is hydrogen or an aromatic group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkynyl group, a phenyl group and a naphthyl group, and R ⁴ is an alkylene group having 1 to 30 carbon atoms. , An alkenylene group, an alkynylene group, a phenylene group and a naphthylene group, and other divalent aromatic groups, which may contain a substituent such as a halogen, a hydroxyl group, an amino group and a carboxyl group.). However, the present invention is not particularly limited to these production methods.

Further, the combustion resistant material in the present invention comprises a cured product of the above silicon-containing polymer compound. The cured product is obtained by melting the silicon polymer compound or dissolving it in a solvent, and then forming the silicon-containing polymer compound into various shapes (molded bodies, films, fibers, etc.), air, nitrogen, argon, helium, etc. It can be obtained by heating in a gas atmosphere. Heating temperature is 100-1000
℃, preferably 100-700 ℃, more preferably 1
It is 50 to 500 ° C. The heating time is not particularly limited,
1 minute to 100 hours. The temperature and time vary depending on the type, shape and form of the silicon-containing polymer compound and the purpose of use of the cured product. The curing reaction can usually be carried out by heating, but other curing agents such as hexamethylenetetramine, diamines, acid anhydrides, or benzoyl peroxide, cumene hydroperoxide, as proposed previously by us,
Radical initiators such as di-t-butyl peroxide, t-butyl perbenzoate, hydrogen peroxide, potassium persulfate, azobisisobutyronitrile, diazoaminoazobenzene (JP-A-6-46941, JP-A-6-46942). Or platinum, iridium, palladium, rhodium, ruthenium,
A catalyst such as a transition metal such as nickel or cobalt or a complex thereof (JP-A-6-45544 and JP-A-6-469).
40) can coexist. It is also possible to coexist with a silicon-containing polymer compound and various polymer compounds such as polyimide, polyamide, phenol resin, epoxy resin, polyether ester ketone, polysulfone and polyoxadiazole.

The flammability-resistant material in the present invention contains the above-mentioned silicon-containing polymer compound or a cured product thereof as a main constituent component, and is used either alone or as a mixture with another material. That is, the flame-resistant material is obtained, for example, by molding a silicon-containing polymer compound or a cured product thereof into a predetermined shape, or by blending or polymer-forming the silicon-containing polymer compound with another polymer compound. Further, it can be obtained by forming a composite material with carbon fiber, silicon carbide fiber, glass fiber and the like. The flame resistant material can also be obtained by a method such as coating the surface of another material with the silicon-containing polymer compound or a cured product thereof.

[0059]

EXAMPLES The present invention will be described below with reference to examples. Example 1 Poly (phenylsilyleneethynylene-1,3-phenyleneethynylene) was synthesized according to the method described in Japanese Patent Application No. 5-43596. In a 10 l glass reaction vessel, Mg
(OH) ₂ was exhausted and calcined at 500 ° C. for 3 hours to remove MgO 4
98 g, 228 g of phenylsilane, 266 g of m-diethynylbenzene, and 4 l of benzene as a solvent were charged. Next, in an argon atmosphere, 30 ° C for 1 hr, 40 ° C for 1 hr, 50 ° C for 1 hr, 60 ° C for 1 hr, and 80 ° C for 2 hr.
The reaction was carried out for a total of 6 hours. After the reaction was completed, the reaction solution was filtered to separate and remove MgO. The solvent in the filtered reaction liquid was distilled off under reduced pressure to such an extent that the polymer was not precipitated, and then the solution was poured into 8 l of hexane to precipitate the polymer. The polymer obtained was dried under reduced pressure at 60 ° C., and finally 319 g
Was obtained as a pale yellow powder (yield 65%). The polymer had a weight average molecular weight of 6,900 and a number average molecular weight of 2,300. Its structure was confirmed by IR and NMR to be structural formula (14) (Chemical Formula 53)

[0060]

Embedded image It turned out to be.

The obtained polymer was heated to 150 ° C. in a nitrogen atmosphere.
It was melted in the above to obtain a molded product (I) having a length of 70 cm, a width of 6.5 cm and a thickness of 3.0 cm. According to TGA, Td ₅ (5% weight loss temperature) of the molded body (I) in argon is 8
The heat resistance was extremely high at 60 ° C., and the specific gravity was 1.14. The TGA of the molded product (I) in air was measured to obtain an index of flammability. Td ₅ was 567 ° C. Also, when the molded body (I) was exposed in the combustion flame of city gas in the air, the heated part of the molded body (I) turned red,
It did not burn, and it returned to its original state by removing the flame.

Example 2 The molded body (I) obtained in Example 1 was further treated with nitrogen atmosphere at 300 ° C., 400 ° C. or 500 ° C. for 2 hours.
Heat treatment was performed to obtain three cured products. There was almost no pyrolysis gas during this heat treatment, and almost no change in shape was observed. According to TGA, the cured product had Td ₅ (5% weight loss temperature) in argon of 860 ° C. and a specific gravity of 1.14. When TGA of the cured product was measured in air, Td ₅ was 567 ° C. The cured product is
None of them burned in the burning flame of city gas in the air. Next, according to Japanese Industrial Standard JIS K 7201, the oxygen index of this cured product (the minimum oxygen concentration necessary for the sample to continue burning) was measured. 300 ° C, 400 ° C or 5
The oxygen indexes of the cured product samples obtained by heat treatment at 00 ° C. were 34, 42 and 55, respectively. Each of these samples burned at an oxygen concentration higher than the oxygen index, but the burning flame was small, the burning rate was slow, and no smoke was observed during burning.

Comparative Examples 1 and 2 Structural formula (50) in which the repeating unit does not have a Si—H bond but has only a C≡C bond or does not have a C≡C bond but has only a Si—H bond. (Chemical 54)

[0064]

[Chemical 54] Or structural formula (51)

[0065]

[Chemical 55] The Td ₅ of two types of polymer compounds represented by The measured values of the silicon-containing polymer represented by Structural Formula (50) and Structural Formula (51) are 525 ° C. and 55, respectively.
It was 0 ° C.

[0066]

Industrial Applicability The present invention provides a novel flammability resistant material containing a silicon-containing polymer compound having a specific structure or a cured product thereof as a main component. The present combustion resistant material can be formed into various shapes by molding, is lightweight and has excellent heat resistance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koji Inoue Mitsui Toatsu Chemical Co., Ltd. 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa

Claims (6)

[Claims] 1. A repeating unit containing at least one Si-
A flammability-resistant material comprising a silicon-containing polymer compound having an H bond and a C≡C bond, or a cured product of the silicon-containing polymer compound. 2. The silicon-containing polymer compound has a structural formula (1):
(Chemical formula 1) [Chemical formula 1] (In the formula, R ¹ is hydrogen or an aromatic group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkynyl group, a phenyl group and a naphthyl group, and these are halogen,
It may contain a substituent such as a hydroxyl group, an amino group or a carboxyl group. ) The flame-resistant material according to claim 1, which is represented by 3. The silicon-containing polymer compound has a structural formula (2):
(Chemical formula 2) [Chemical formula 2] (In the formula, R ² is hydrogen or an aromatic group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkynyl group, a phenyl group and a naphthyl group, and these are halogen,
It may contain a substituent such as a hydroxyl group, an amino group or a carboxyl group. ) The flame-resistant material according to claim 1, which is represented by 4. The silicon-containing polymer compound has a structural formula (3):
(Chemical Formula 3) [Chemical Formula 3] (In the formula, R ³ is hydrogen or an aromatic group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkynyl group, a phenyl group and a naphthyl group, and R ⁴ is an alkylene group having 1 to 30 carbon atoms. , An alkenylene group, an alkynylene group, a phenylene group, a naphthylene group, or another divalent aromatic group, which may contain a substituent such as a halogen, a hydroxyl group, an amino group, or a carboxyl group.). The combustion resistant material according to claim 1, which is a material. 5. The silicon-containing polymer compound has a weight average molecular weight of 500 to 1,000,000.
The flammability resistant material according to 2, 3 or 4. 6. The flame resistant material according to claim 1, wherein the cured product of the silicon-containing polymer compound is a cured product obtained by heat-treating the silicon-containing polymer compound at a temperature of 100 to 1000 ° C.