JPH09143268A - Silicon-based polymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a silicone-based polymer, excellent in photoreactivity, heat resistance and flame retardance and useful for aerospace materials, a building material, etc., by carrying out the polycondensation of a dimetalated diethynylbenzene derivative and a specific dimetalated substance with a dihalosilane derivative. SOLUTION: The polycondensation reaction of a diethynylbenzene derivative represented by formula I [R<1> is H, a 1-20C alkyl, a 6-12C aryl or a group represented by the formula R<2> 3 Si (R<2> is H, a 1-20C alkyl or a 6-12C aryl); M is Li, Na, K, MgX (X is a halogen), CaX, CuX or HgX] and a dimetalated substance represented by the formula M-Z-M (Z is O, a 60-30C arylene derivative or a 2-4C acetylene derivative) with a dihalosilane derivative represented by formula II [Y is same kind as that of Z; (n) is 1-19] to afford the objective silicon-based polymer comprising constituent units, represented by formulas III, IV and V at ratios of (a), (b) and (c) [0<(a), (b) and (c)<1] and satisfying formulas [(a)+(b)+(c)=1, (1:99) to (99:1) ratio of (a):(b) and (1:2) to (2:1) ratio of [(a)+(b)]:(c) and having >=500 weight-average molecular weight.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silicon-based polymer and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, many silicon compounds have been proposed as functional materials having excellent heat resistance. For example,
A polymer compound containing an aromatic ring and an acetylene (C≡C triple bond) unit is synthesized by a polycondensation reaction between a disodium salt of aromatic diacetylene and a dichlorosilane derivative [J. Organomet. Chem. 260,171 ( 1984)]. A similar polymer can also be obtained by a polycondensation reaction of a diethynylsilane compound and an aromatic dihalide [J. Polym. Sc
i.Part C: Polym. Lett., 28, 431 (1990)].

Further, as a polymer compound containing a siloxane unit, a polymer compound containing p-phenylene [J.
Poly.Sci .: Part A 2, 15 (1964)], acetylene-containing polymer compound [Eur. Poly.J. 28, 1373 (1992)] and diacetylene-containing polymer compound (U.S. Pat.No. 3,714,118), etc. It is synthesized. However, none of the above silicon compounds has sufficient photoreactivity, heat resistance and flame retardancy.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and an object of the present invention is to provide a silicon polymer excellent in photoreactivity, heat resistance and flame retardancy, and a method for producing the same.

[0005]

In the silicon-based polymer of the present invention, the structural units represented by the general formulas (1), (2) and (3) satisfy a specific relationship of a, b and c. And the weight average molecular weight is 500 or more.

[0006]

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[0007]

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[0008]

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In the general formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a silyl group represented by R ² ₃ Si and is the same. It may or may not be.

In the general formula (2), Z represents an arylene derivative having 6 to 30 carbon atoms or an acetylene derivative having 2 to 4 carbon atoms.

In the general formulas (1) and (3), R ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or 6 to 12 carbon atoms.
Represents an aryl group and may be the same or different. In general formula (3), Y is an oxygen atom and has 6 to 30 carbon atoms.
Or an acetylene derivative having 2 to 4 carbon atoms, and n is an integer of 1 to 19.

The carbon number of the alkyl group represented by R ¹ and R ² is limited to 1 to 20 because the bond is likely to be broken and the heat resistance of the obtained silicon-based compound is lowered when the number is large. Examples of the alkyl group represented by R ¹ and R ² include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Examples thereof include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and an eicodecyl group.

The number of carbon atoms of the aryl group represented by R ¹ and R ² is limited to 6 to 12 because the solubility in a solvent decreases as the number increases. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a biphenylyl group, and a naphthyl group.

Examples of the silyl group represented by R ² ₃ Si include trimethylsilyl group, triethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, diphenylmethylsilyl group, methylsilyl group, dimethylsilyl group, phenylsilyl group, Examples thereof include diphenylsilyl group and methylphenylsilyl group.

Examples of the arylene derivative having 6 to 30 carbon atoms represented by Z include phenylene, biphenylene, terphenylene, quarter phenylene and substituted products thereof. As the acetylene derivative having 2 to 4 carbon atoms,
Examples include acetylene and diacetylene.

Examples of the arylene derivative having 6 to 30 carbon atoms represented by Y include phenylene, biphenylene, terphenylene, quarter phenylene and substituted products thereof. As the acetylene derivative having 2 to 4 carbon atoms,
Examples include acetylene and diacetylene.

When the above-mentioned n becomes large, sufficient heat resistance and flame retardancy cannot be obtained, so that it is limited to an integer of 1 to 19.

In the silicon-based polymer of the present invention, the structural units represented by the general formulas (1), (2) and (3) are a,
It is contained in the respective proportions of b and c. When the proportion of a is reduced, heat resistance due to crosslinking is lost, when the proportion of b is reduced, flame retardancy is lost, and when the proportion of c is reduced, moldability is impaired. Moreover, when the ratio of (a + b) decreases, heat resistance and flame retardancy are lost.

Therefore, the above a, b and c are the following (a)
It is limited to the range that satisfies the relational expression of (c). a + b + c = 1 (a) a: b = 1: 99 to 99: 1 (b) (a + b): c = 1: 2 to 2: 1 (c) where 0 < a, b, c <1.

The weight average molecular weight of the above silicon-based polymer is
If it becomes smaller, sufficient heat resistance and flame retardancy cannot be obtained, so it is limited to 500 or more, and if it becomes larger, solubility in a solvent decreases and handling becomes difficult, so there is no particular limitation, but it is several million or less. preferable.

Next, the method for producing the silicon compound of the present invention 2 will be described. The production method of the present invention 2 is a method for producing a silicon-based compound of the present invention, which comprises a dimetallated product of a diethynylbenzene derivative represented by the general formula (4) and a dimetallated product represented by the general formula (5). It is obtained by polycondensing the mixture with the dihalosilane derivative represented by the general formula (6).

[0022]

[Formula 10]

[0023]

[Formula 11]

[0024]

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In the general formula (4), R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a silyl group represented by R ² ₃ Si and is the same. It may or may not be.

In the general formulas (4) and (5), M is Li, N
a, K, MgX, CaX, CuX, HgX and other metal atoms or metal halides. X represents a halogen atom. In general formula (5), Z represents oxygen, an arylene derivative having 6 to 30 carbon atoms or an acetylene derivative having 2 to 4 carbon atoms.

In the general formulas (4) and (6), R ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or 6 to 12 carbon atoms.
Represents an aryl group and may be the same or different. In formula (6), X represents a halogen atom and Y represents
It shows an arylene derivative having 6 to 30 carbon atoms or an acetylene derivative having 2 to 4 carbon atoms, and n represents an integer of 1 to 19.

As R ¹ , R ² , Z and Y, the same components as in the first invention can be mentioned.

The mixture of the dimetallated derivative of the diethynylbenzene derivative represented by the general formula (4) and the dimetallated derivative represented by the general formula (5) is the same as the diethynylbenzene derivative represented by the general formula (7). It is obtained by reacting the dihalide represented by the general formula (8) or the acetylene derivative represented by the general formula (9) with a metallizing agent.

[0030]

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[0031]

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[0032]

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In the above general formula (7), W represents a hydrogen atom or a trimethylsilyl group.

Examples of the above-mentioned diethynylbenzene derivative (7) include 1,4-diethynylbenzene, 1,4-diethynyl-2-methylbenzene, 1,4-diethynyl-2,3-dimethylbenzene, 1,4-diethynyl 2, 5-dimethylbenzene, 1,4-diethynyl-2,6-dimethylbenzene, 1,4-diethynyl-3,5-dimethylbenzene, 1,4-diethynyl-2,3,5,6-tetramethylbenzene, 1 1,4-diethynyl-2- (trimethylsilyl) benzene, 1,4-diethynyl-2,3-bis (trimethylsilyl) benzene, 1,4-diethynyl 2,5-bis (trimethylsilyl) benzene, 1,4-diethynyl 2,6 -Bis (trimethylsilyl) benzene, 1,4-diethynyl-2,3,5,6-tetrakis (trimethylsilyl) benzene, 1,3-diethynylbenzene, 1,3-diethynyl-2-methylbenzene, 1,3-diethynyl-4-methylbenzene , 1,3-diethynyl-5-methylbenzene, 1 , 3-diethynyl-2,4-dimethylbenzene, 1,3-
Diethynyl-2,5-dimethylbenzene, 1,3-diethynyl-4,
5-dimethylbenzene, 1,3-diethynyl-4,6-dimethylbenzene, 1,3-diethynyl-2,4,5,6-tetramethylbenzene, 1,3-diethynyl-2- (trimethylsilyl) benzene, 1, 3-diethynyl-4- (trimethylsilyl) benzene, 1,3-diethynyl-5- (trimethylsilyl) benzene, 1,3-diethynyl-2,4-bis (trimethylsilyl) benzene, 1,3-diethynyl-2,5-bis ( (Trimethylsilyl) benzene, 1,3-diethynyl-4,5-bis (trimethylsilyl) benzene, 1,3-diethynyl-4,6-bis (trimethylsilyl) benzene, 1,3-diethynyl-2,4,5,6- Tetrakis (trimethylsilyl) benzene, 1,2-diethynylbenzene, 1,2-diethynyl-3-methylbenzene, 1,2-diethynyl-4-methylbenzene, 1,2-diethynyl-3,4-dimethylbenzene, 1,2-diethynyl 3, 5-dimethylbenzene,
1,2-diethynyl-3,6-dimethylbenzene, 1,2-diethynyl-4,5-dimethylbenzene, 1,2-diethynyl-3,4,5,6-tetramethylbenzene, 1,2-diethynyl Benzene, 1,2-diethynyl-3- (trimethylsilyl) benzene, 1,2-diethynyl-4- (trimethylsilyl) benzene, 1,2-diethynyl-3,4-bis (trimethylsilyl) benzene, 1,2-diethynyl 3,5 -Bis (trimethylsilyl) benzene, 1,2-
Diethynyl-3,6-bis (trimethylsilyl) benzene,
1,2-diethynyl-4,5-bis (trimethylsilyl) benzene, 1,2-diethynyl-3,4,5,6-tetrakis (trimethylsilyl) benzene, 1,4-bis (trimethylsilylethynyl) benzene, 1,4 -Bis (trimethylsilylethynyl)
-2-Methylbenzene, 1,4-bis (trimethylsilylethynyl) -2,3-dimethylbenzene, 1,4-bis (trimethylsilylethynyl) 2,5-dimethylbenzene, 1,4-bis (trimethylsilylethynyl) -2,6 -Dimethylbenzene, 1,4
-Bis (trimethylsilylethynyl) -3,5-dimethylbenzene, 1,4-bis (trimethylsilylethynyl) -2,3,5,6
-Tetramethylbenzene, 1,4-bis (trimethylsilylethynyl) -2- (trimethylsilyl) benzene, 1,4-bis (trimethylsilylethynyl) -2,3-bis (trimethylsilyl) benzene, 1,4-bis (trimethylsilylethynyl) ) 2,5-bis (trimethylsilyl) benzene, 1,4-bis (trimethylsilylethynyl) 2,6-bis (trimethylsilyl) benzene, 1,4-bis (trimethylsilylethynyl) -2,3,5,6-tetrakis ( Trimethylsilyl) benzene, 1,3-bis (trimethylsilylethynyl) benzene,
1,3-bis (trimethylsilylethynyl) -2-methylbenzene, 1,3-bis (trimethylsilylethynyl) -4-methylbenzene, 1,3-bis (trimethylsilylethynyl) -5
-Methylbenzene, 1,3-bis (trimethylsilylethynyl) -2,4-dimethylbenzene, 1,3-bis (trimethylsilylethynyl) -2,5-dimethylbenzene, 1,3-bis (trimethylsilylethynyl) -4,5- Dimethylbenzene, 1,3
-Bis (trimethylsilylethynyl) -4,6-dimethylbenzene, 1,3-bis (trimethylsilylethynyl) -2,4,5,6
-Tetramethylbenzene, 1,3-bis (trimethylsilylethynyl) -2- (trimethylsilyl) benzene, 1,3-bis (trimethylsilylethynyl) -4- (trimethylsilyl) benzene, 1,3-bis (trimethylsilylethynyl)
-5- (Trimethylsilyl) benzene, 1,3-bis (trimethylsilylethynyl) -2,4-bis (trimethylsilyl)
Benzene, 1,3-bis (trimethylsilylethynyl) -2,5
-Bis (trimethylsilyl) benzene, 1,3-bis (trimethylsilylethynyl) -4,5-bis (trimethylsilyl) benzene, 1,3-bis (trimethylsilylethynyl)
-4,6-bis (trimethylsilyl) benzene, 1,3-bis (trimethylsilylethynyl) -2,4,5,6-tetrakis (trimethylsilyl) benzene, 1,2-bis (trimethylsilylethynyl) benzene, 1,2- Bis (trimethylsilylethynyl) -3-methylbenzene, 1,2-bis (trimethylsilylethynyl) -4-methylbenzene, 1,2-bis (trimethylsilylethynyl) -3,4-dimethylbenzene, 1,2
-Bis (trimethylsilylethynyl) -3,5-dimethylbenzene, 1,2-bis (trimethylsilylethynyl) -3,6-dimethylbenzene, 1,2-bis (trimethylsilylethynyl) -4,5-dimethylbenzene, 1, 2-bis (trimethylsilylethynyl) -3,4,5,6-tetramethylbenzene, 1,2-
Bis (trimethylsilylethynyl) benzene, 1,2-bis (trimethylsilylethynyl) -3- (trimethylsilyl) benzene, 1,2-bis (trimethylsilylethynyl)
-4- (Trimethylsilyl) benzene, 1,2-bis (trimethylsilylethynyl) -3,4-bis (trimethylsilyl)
Benzene, 1,2-bis (trimethylsilylethynyl) -3,5
-Bis (trimethylsilyl) benzene, 1,2-bis (trimethylsilylethynyl) -3,6-bis (trimethylsilyl) benzene, 1,2-bis (trimethylsilylethynyl)
Examples include -4,5-bis (trimethylsilyl) benzene and 1,2-bis (trimethylsilylethynyl) -3,4,5,6-tetrakis (trimethylsilyl) benzene.

Examples of the dihalide (8) include 1,4-diiodobenzene, 1,4-diiodo-2-methylbenzene, 1,4-diiodo-2,3-dimethylbenzene, 1,4- Diiodo-2,5-dimethylbenzene, 1,4-diiodo-2,6-dimethylbenzene, 1,4-diiodo-3,5-dimethylbenzene,
1,4-diiodo-2,3,5,6-tetramethylbenzene, 1,4-diiodo-2- (trimethylsilyl) benzene, 1,4-diiodo-2,3-bis (trimethylsilyl) benzene, 1,4 -Diiodo-2,5-bis (trimethylsilyl) benzene, 1,4-
Diiodo-2,6-bis (trimethylsilyl) benzene, 1,4
-Diiodo-2,3,5,6-tetrakis (trimethylsilyl) benzene, 1,3-diiodobenzene, 1,3-diiodo-2-methylbenzene, 1,3-diiodo-4-methylbenzene, 1,3 -Diiodo-5-methylbenzene, 1,3-diiodo-2,4-dimethylbenzene, 1,3-diiodo-2,5-dimethylbenzene, 1,3-
Diiodo-4,5-dimethylbenzene, 1,3-diiodo-4,6-dimethylbenzene, 1,3-diiodo-2,4,5,6-tetramethylbenzene, 1,3-diiodo-2- (trimethylsilyl ) Benzene, 1,3-diiodo-4- (trimethylsilyl) benzene, 1,3-diiodo-5- (trimethylsilyl) benzene,
1,3-diiodo-2,4-bis (trimethylsilyl) benzene, 1,3-diiodo-2,5-bis (trimethylsilyl) benzene, 1,3-diiodo-4,5-bis (trimethylsilyl) benzene, 1, 3-diiodo-4,6-bis (trimethylsilyl)
Benzene, 1,3-diiodo-2,4,5,6-tetrakis (trimethylsilyl) benzene, 1,2-diiodobenzene, 1,2-diiodo-3-methylbenzene, 1,2-diiodo-4-methyl Benzene, 1,2-diiodo-3,4-dimethylbenzene, 1,2-diiodo-3,5-dimethylbenzene, 1,2-diiodo-3,6-dimethylbenzene, 1,2-diiodo-4,5 -Dimethylbenzene, 1,2
-Diiodo-3,4,5,6-tetramethylbenzene, 1,2-diiodobenzene, 1,2-diiodo-3- (trimethylsilyl) benzene, 1,2-diiodo-4- (trimethylsilyl) benzene, 1, 2-diiodo-3,4-bis (trimethylsilyl) benzene, 1,2-diiodo-3,5-bis (trimethylsilyl) benzene, 1,2-diiodo-3,6-bis (trimethylsilyl)
Iodides such as benzene, 1,2-diiodo-4,5-bis (trimethylsilyl) benzene and 1,2-diiodo-3,4,5,6-tetrakis (trimethylsilyl) benzene, and their chlorides, bromides, fluorides And dihalobenzene derivatives such as phenylene, biphenylene, terphenylene, quarterphenylene and its substituted iodides, and their chlorides, bromides and fluorides.

Examples of the acetylene derivative (9) include acetylene, diacetylene and trimethylsilyl-substituted products thereof.

Examples of the metallizing agent include butyllithium, methyllithium, phenyllithium, ethylmagnesium bromide, sodium hydride, calcium hydride and the like.

When the amount of the metallizing agent used is small or large, the molecular weight of the obtained silicon-based polymer decreases, and sufficient heat resistance cannot be obtained. On the other hand, the molar number is preferably 1 to 4 times, and more preferably 1.5 to 3 times.

The above polycondensation reaction is preferably carried out in a solvent, which may be polar or non-polar, but is preferably an aprotic solvent such as tetrahydrofuran, diethyl ether, toluene, xylene or hexane. , And more preferably tetrahydrofuran.

The reaction temperature of the polycondensation reaction is not particularly limited, but a temperature between -150 ° C. and the boiling point of the solvent used is preferable. When using tetrahydrofuran as the solvent, a reaction temperature of −50 to 70 ° C. is particularly preferable.

The polycondensation reaction proceeds in either air or an inert gas atmosphere, but it is particularly preferably carried out in an argon or nitrogen atmosphere. If the reaction time is short or long, the yield of the silicon-based compound obtained decreases, so that it is preferably 1 to 48 hours.

A catalyst may be used in the above polycondensation reaction,
Examples of the catalyst include hydrochloric acid, n-hexylamine-2-hexanoate, tetramethylguanidine di-2-hexanoate, etc., but are not limited thereto.

If the amount of the above catalyst used decreases, the reactivity of the polycondensation reaction system decreases, and if it increases, it tends to remain in the obtained silicon-based polymer, resulting in deterioration of the physical properties. Therefore, 100 parts by weight of the diethynylbenzene derivative. Against 0.00
1 to 10 parts by weight is preferable, and more preferably 0.01 to
1 part by weight.

The silicon-based polymer of the first invention is obtained by polycondensing the mixture of at least two dimetal compounds obtained above with the dihalosilane derivative represented by the general formula (6).

Examples of the dihalosilane derivative include 1,3-dichloro-1,1,3,3-tetramethyldisiloxane and 1,3-dichloro-, when Y is an oxygen atom in the general formula (6).
1,1,3,3-tetraphenyldisiloxane, 1,3-dichloro-
1,3-dimethyl-1,3-diphenyldisiloxane, 1,5-dichloro-1,1,3,3,5,5-hexamethyltrisiloxane, 1,5-
Dichloro-1,1,3,3,5,5-hexaphenyltrisiloxane, 1,5-dichloro-1,3,5-trimethyl-1,3,5-triphenyltrisiloxane, 1,7-dichloro- 1,1,3,3,5,5,7,7-octamethyltrisiloxane, 1,5-dichloro-1,1,3,3,5,
5,7,7-Octaphenyltrisiloxane, 1,5-dichloro-
Chlorides such as 1,3,5,7-tetramethyl-1,3,5,7-tetraphenyltrisiloxane and bischlorosilane derivatives such as bromides, iodides and fluorides thereof; Y has 6 to 30 carbon atoms
In the case of the arylene derivative of, phenylene, biphenylene, terphenylene, quarter phenylene and its substitution products, and the like; when Y is an acetylene derivative structure having 2 to 4 carbon atoms, acetylene and diacetylene can be mentioned.

In the above polycondensation reaction, it is also preferable to add at least one additive selected from lithium halide, amine polydentate ligand and crown ether. Examples of the additive include lithium chloride and odor. Lithium halides such as lithium iodide, lithium fluoride and lithium iodide; amine-based polydentate ligands such as tetramethylethylenediamine, hexamethylphosphoric triamide, hexamethylphosphorus triamide; 12-crown-4 ( 1,4,7,10-Tetraoxacyclododecane), 15-crown-5 (1,4,7,10,13-
Pentaoxacyclopentadecane), 18-crown-
6 (1,4,7,10,13,16-hexaoxacyclooctadecane) and other crown ethers.

When the amount of the above-mentioned additive used is small, the reaction system cannot be sufficiently activated, and when it is large, it becomes difficult to remove it from the reaction product. Therefore, it is 0 relative to the number of moles of the dihalosilane derivative. The molar number is preferably 0.0001 to 100 times, and more preferably 0.01 to 10 times.

[0048]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. (Example 1) Argon-substituted reaction vessel (Dean Stark type)
0.27 g of magnesium pieces was placed in 4, and 4,4'-dibromobiphenyl dissolved in 10 ml of tetrahydrofuran.
6 g was added with vigorous stirring to cause Grignard reaction, and further diluted with 5 ml of tetrahydrofuran, then 60
Aging at ℃ for 5 hours. Separately, 0.63 g of 1,4-diethynylbenzene was dissolved in 15 ml of tetrahydrofuran and placed in a reaction vessel (Dean Stark type) whose atmosphere was replaced with argon, and 1.7 ml of a 3 molar concentrated ethylmagnesium bromide / hexane solution was added dropwise. Aging at room temperature for 2 hours. Both are suspended by the precipitated salt, but after mixing as it is,
4.5 g of dichlorotetraphenyldisiloxane dissolved in 5 ml of tetrahydrofuran is added dropwise, and the mixture is stirred at 60 ° C. for 24 hours. The reaction mixture is poured into aqueous ammonium chloride solution, extracted with tetrahydrofuran and ethyl ether, and washed with ion-exchanged water and saturated saline. After drying over anhydrous magnesium sulfate, the solution was concentrated and reprecipitated with isopropyl alcohol for purification, and a silicon-based polymer powder was used.
8 g were obtained.

The structure of the obtained silicon-based polymer was identified by the following measurements. (A) IR spectrum IR spectrum (IR spectrum "270 manufactured by Hitachi, Ltd.
-30 "), as shown in FIG.
Absorption of stretching vibration of the cc triple bond of disubstituted acetylene was sharply observed at around 160 cm ^-1 . In addition, 1
Broad absorption attributed to the Si-O-Si bond was observed at 120 cm- ¹ . It was also found that the other peaks were derived from the aromatic ring.

(B) Proton NMR spectrum Proton NMR spectrum (FT-NM manufactured by Hitachi Ltd.)
R, measured using "RT-9000 type")
As shown in, almost no silanol group protons were observed, but aromatic protons were observed at 7 to 8 ppm.

(C) Molecular weight The GPC was measured using "GPC-8000" manufactured by Tosoh Corporation, and the result was 5,000 in terms of polystyrene.

(D) Thermogravimetric analysis Using “TAS-300” manufactured by Rigaku, the temperature was raised from 30 ° C. to 800 ° C. at a temperature rising rate of 10 ° C./min, and 5% by weight and 10% with respect to the initial weight. Temperature when weight% is reduced to 3
It was found to be 55 ° C. and 503 ° C., and the weight residual ratio at 800 ° C. was 63% by weight.

[0053]

The constitution of the silicon-based polymer of the present invention is as described above, and therefore it is excellent in photoreactivity, heat resistance and flame retardancy and is suitable for use in aerospace materials, building materials and the like. . Further, the method for producing a silicon-based compound of the present invention 2 provides a silicon-based polymer having excellent photoreactivity, heat resistance and flame retardancy.

[Brief description of the drawings]

FIG. 1 is a chart showing an IR spectrum of a silicon-based polymer obtained in an example.

FIG. 2 is the proton N of the silicon-based polymer obtained in the example.
It is a chart which shows MR.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuhiro Okada 2-1 Hyakusan, Shimamoto-cho, Mishima-gun, Osaka Prefecture Sekisui Chemical Co., Ltd.

Claims (2)

[Claims] 1. Structural units represented by general formulas (1), (2) and (3) are a, b and c (provided that 0 <a, b, c <
1) A silicon-based polymer which is contained in the respective proportions of 1), wherein a, b and c are the following (a), (b) and (c):
And a weight-average molecular weight of 500 or more. a + b + c = 1 (b) a: b = 1: 99 to 99: 1 (b) (a + b): c = 1: 2 to 2: 1 (c) Embedded image Embedded image (In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a silyl group represented by R ² ₃ Si, which may be the same or different. R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, and may be the same or different, and Z is an arylene derivative having 6 to 30 carbon atoms. Or, the acetylene derivative structure having 2 to 4 carbon atoms,
Y represents oxygen, an arylene derivative having 6 to 30 carbon atoms or an acetylene derivative structure having 2 to 4 carbon atoms, and n is 1 to 19
Indicates an integer) 2. A mixture of a diethynylbenzene derivative dimetallated compound represented by the general formula (4) and a dimetallated compound represented by the general formula (5) is polycondensed with a dihalosilane derivative represented by the general formula (6). The method for producing a silicon-based polymer according to claim 1, wherein Embedded image Embedded image [Chemical 6] (In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a silyl group represented by R ² ₃ Si, which may be the same or different. R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, and may be the same or different, and Y is arylene having 6 to 30 carbon atoms. A derivative or an acetylene derivative structure having 2 to 4 carbon atoms, Z represents oxygen, an arylene derivative having 6 to 30 carbon atoms or an acetylene derivative structure having 2 to 4 carbon atoms, and n is 1 to 1
An integer of 19 is shown. Furthermore, M is Li, Na, K, Mg
A metal atom or metal halide of X, CaX, CuX, HgX is shown. X represents a halogen atom)