JPH10273534A - Silicon-based polymer, method for producing the same, and cured silicon-based resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel silicon-based polymer having a functional group in a side chain having high heat resistance, a method for producing the same, and a cured silicon-based resin. SOLUTION: The silicon-based polymer has a structure represented by the general formula (1) as a constitutional unit and has a weight average molecular weight of 500 or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicon polymer useful as a functional material having excellent conductivity, photoreactivity, heat resistance and flame retardancy, a method for producing the same, and a cured silicon resin. is there.

[0002]

2. Description of the Related Art Due to the properties of silicon, silicon-based polymers have attracted attention as photochemical and electrical functional materials or structural materials such as heat resistance and flame retardancy, and have been actively studied. However, there are few reports on silicon-based polymers having a functional group in a side chain.

[0003] Ishikawa et al. Have a polymer having a Si-H group in the side chain (Macromolecules, 1994, 27, 5583), or S
Polymers having i-OEt groups (Polymer Preprints, J
apan, 1995, 44, 2051) and reported on its reaction and heat resistance. Although these polymers exhibit relatively high heat resistance, few have a 5% weight loss temperature of more than 500 ° C. in thermogravimetric analysis, and are not necessarily sufficient in heat resistance. In addition, there are almost no silicon-based polymers having a functional group, and development of a novel high heat-resistant polymer is expected.

The method for producing the above polymer is not a simple method because hydrochlorosilane, which is relatively difficult to handle, is used, and it is difficult to synthesize monomeric hydrochlorosilane and ethoxysilane. For this reason, there has been a demand for a method for producing a silicon-based polymer having a functional group in a side chain more simply than before.

[0005]

SUMMARY OF THE INVENTION In view of the above drawbacks, the present invention provides a novel silicon-based polymer having a high heat resistance and containing a functional group in a side chain, a method for producing the same, and a cured silicon-based resin. The purpose is to do so.

[0006]

The silicon-based polymer according to the first aspect of the present invention (hereinafter referred to as the first aspect of the present invention) has a structure represented by the general formula (1) as a structural unit, and The weight average molecular weight is 500 or more.

The method for producing a silicon-based polymer according to the second aspect of the present invention (hereinafter referred to as the second invention) is a method for producing a silicon-based polymer according to the first aspect of the present invention, which comprises the general formula (2) ) Is reacted with a metal compound of a diethynylbenzene derivative represented by the general formula (3) or (4), and then reacted with a metal represented by the general formula (5). It is characterized by reacting with any one or more of compounds, water and alcohol.

The method for producing a silicon-based polymer according to the third aspect of the present invention (hereinafter referred to as the third aspect of the present invention) is a method for producing a silicon-based polymer according to the first aspect of the present invention, which comprises the general formula (6) ) Is reacted with a diethynylsilane compound represented by the general formula (7) in the presence of a transition metal catalyst.

The cured product of the silicon-based resin according to the invention described in claim 4 of the present invention (hereinafter, referred to as “invention 4”) is the present invention.
3. The silicon-based polymer according to any one of 3. above, which is cured.

Hereinafter, the present invention 1 will be described in detail.
The silicon-based polymer of the first aspect of the present invention has a structural unit represented by the general formula (1) as a structural unit.

[0011]

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In the formula, R ¹ is a hydrogen atom, having 1 to 20 carbon atoms.
Represents an alkyl group or an aryl group having 6 to 30 carbon atoms,
They may be the same or different, and the bonding position between R ¹ and the benzene ring is a carbon other than the carbon substituted by the ethynyl group.

In the formula, R ² represents an acetylene derivative group having 2 to 20 carbon atoms.

Wherein R ³ is a hydrogen atom, having 1 to 20 carbon atoms.
And an aryl group having 6 to 30 carbon atoms or an acetylene derivative group having 2 to 20 carbon atoms, and R ² and R ³ may be the same.

When the number of carbon atoms of R ^{1 to} R ³ is a substituent having an alkyl group, if the number of carbon atoms increases, the bond becomes liable to be broken and the heat resistance of the resulting silicon-based polymer decreases. In the case of a group, the solubility of the polymer in a solvent is reduced, so that the group is limited to the above range.

Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Examples include, but are not limited to, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicodecyl and the like.

Examples of the aryl group include, but are not limited to, a phenyl group, a tolyl group, a xylyl group, a biphenyl group and a naphthyl group.

The acetylene derivative group includes ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, noninyl group,
Decynyl group, undecynyl group, dodecynyl group, tridecynyl group, tetradecynyl group, pentadecynyl group, hexadecynyl group, heptadecynyl group, octadecynyl group, nonadecinyl group, eicodecinyl group, phenylethynyl group, tolyethynyl group, xylylethynyl group, biphenylethynyl group, Examples include, but are not limited to, naphthylethynyl, ethynylphenyl, ethynylbiphenyl, trimethylsilylethynyl, triphenylsilylethynyl, and the like.

The weight average molecular weight of the silicon-based polymer is:
If it is smaller, sufficient heat resistance and moldability cannot be obtained, so that the number is limited to 500 or more. The upper limit of the weight-average molecular weight is not particularly limited, but if it is too large, the solubility in a solvent will be low.

The silicon-based polymer of the present invention 1 has a functional group in a side chain, and exhibits high heat resistance because it is networked by a cross-linking reaction between the side chains.

Next, the method for producing the silicon-based polymer of the present invention 2 will be described. The present invention 2 is the production method of the present invention 1, wherein a metal compound of a diethynylbenzene derivative represented by the general formula (2) and a silyl halide represented by the general formula (3) or (4) are provided. After reacting with the compound, the compound is reacted with at least one of the metal compound represented by the general formula (5), water and alcohol.

[0022]

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[0023]

[Formula 10]

[0024]

[Formula 11]

[0025]

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In the formula, R ¹ is a hydrogen atom, having 1 to 20 carbon atoms.
Represents an alkyl group or an aryl group having 6 to 30 carbon atoms,
They may be the same or different, and the bonding position between R ¹ and the benzene ring is a carbon other than the carbon substituted by the ethynyl group.

In the formula, R ³ is a hydrogen atom, having 1 to 20 carbon atoms.
And an aryl group having 6 to 30 carbon atoms or an acetylene derivative group having 2 to 20 carbon atoms, and X ¹ represents a halogen atom.

In the formula, R ² represents an acetylene derivative group having 2 to 20 carbon atoms, and R ² and R ³ may be the same.
M ¹ and M ^{2 each} represent a halide of an alkali metal or an alkaline earth metal.

In the production method of the present invention 2, first, a metal unit of an organometallic compound of a diethynylbenzene derivative and two halogen atom units in a silyl halide compound react to form a polymer having a halogen atom in a side chain. Is generated, followed by reacting the polymer with one or more of a metal compound, water and an alcohol, whereby a halogen atom is replaced by an R ² group, and a polymer of the present invention 1 is obtained.

The number of carbon atoms of R ^{1 to} R ³ is limited to the above-mentioned range for the same reason as in the first embodiment, and examples thereof include those similar to the first embodiment.

Examples of the halogen atom represented by X ¹ include fluorine, chlorine, bromine and iodine, with chlorine being preferred.

Examples of the alkali metal represented by M ¹ and M ² include lithium, sodium, potassium and the like, and examples of the halide of the alkaline earth metal include:
Examples include, but are not limited to, magnesium bromide, calcium bromide, and the like.

Examples of the halogenated silyl compound represented by the general formula (3) include, for example, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, butyltrichlorosilane, pentyltrichlorosilane, hexyltrichlorosilane, heptyltrichlorosilane,
Octyltrichlorosilane, nonyltrichlorosilane,
Decyltrichlorosilane, undecyltrichlorosilane, dodecyltrichlorosilane, tridecyltrichlorosilane, tetradecyltrichlorosilane, pentadecyltrichlorosilane, hexadecyltrichlorosilane, heptadecyltrichlorosilane, octadecyltrichlorosilane, nonadecyltrichlorosilane, eicodecyltri Examples include, but are not limited to, chlorosilane, phenyltrichlorosilane, tolyltrichlorosilane, xylyltrichlorosilane, biphenyltrichlorosilane, naphthyltrichlorosilane, and their corresponding fluorides, bromides, and iodides.

Examples of the halogenated silyl compound represented by the general formula (4) include tetrachlorosilane, tetrafluorosilane, tetrabromosilane, tetraiodosilane and the like.

Examples of the metal compound represented by the general formula (5) include ethynyl magnesium bromide, propynyl magnesium bromide, butynyl magnesium bromide, pentynyl magnesium bromide, hexynyl magnesium bromide, heptynyl magnesium bromide, octynyl Magnesium bromide, noninyl magnesium bromide, decynyl magnesium bromide, undecinyl magnesium bromide, dodecinyl magnesium bromide, tridecinyl magnesium bromide, tetradecynyl magnesium bromide, pentadecynyl magnesium bromide, hexadecynyl magnesium bromide, heptadecinyl Magnesium bromide, octadecynyl magnesium bromide, nonadesini Magnesium bromide, eicodecinyl magnesium bromide, phenylethynyl magnesium bromide, tolylethynyl magnesium bromide, xylylethynyl magnesium bromide, biphenylethynyl magnesium bromide, naphthylethynyl magnesium bromide, ethynylphenyl magnesium bromide, ethynylbiphenyl magnesium bromide, trimethylsilylethynyl magnesium bromide Triphenylsilylethynyl magnesium bromide, vinyl magnesium bromide, allyl magnesium bromide, propenyl magnesium bromide, butenyl magnesium bromide, pentenyl magnesium bromide, hexenyl magnesium bromide, heptenyl magnesium bromide Octenyl magnesium bromide, nonenyl magnesium bromide, decenyl magnesium bromide, undecenyl magnesium bromide, dodecenyl magnesium bromide, tridecenyl magnesium bromide, tetradecenyl magnesium bromide, pentadecenyl magnesium bromide , Hexadecenyl magnesium bromide, heptadecenyl magnesium bromide, octadecenyl magnesium bromide, nonadecenyl magnesium bromide, eicodecenyl magnesium bromide, phenyl vinyl magnesium bromide, tolyl vinyl magnesium bromide, xylyl vinyl magnesium Bromide, biphenyl vinyl magnesium bromide, naphthyl vinyl magnesium bromide, vinyl Organometallic compounds such as ruphenylmagnesium bromide, vinylbiphenylmagnesium bromide and the corresponding lithium, sodium and potassium compounds, and sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, sodium pentoxide, sodium hexoxide , Sodium heptoxide, sodium octoxide, sodium nonoxide, sodium decoxide, sodium undecoxide, sodium dodecoxide, sodium tridecoxide, sodium tetradecoxide, sodium pentadecoxide, sodium hexadecoxide, sodium Heptadecoxide, sodium octadecoxide, sodium nonadecoxide, sodium eicodecoxide, sodium Mufenokishido, trisodium Loki Sid, sodium key siloxides, sodium bi phenoxide, lithium corresponding to sodium naphthoquinone butoxide and these, an inorganic metal compound such as potassium compounds include, but are not limited to.

The alcohol used in the present invention 2 includes, for example, methanol, ethanol, propanol,
Butanol, pentanol, hexanol, heptanol, octanol, nonanol, desanol, undesanol, dodesanol, tridesanol, tetradesanol, pentadesanol, hexadesanol, heptadesanol, octadesanol, nonadesanol, eicodesanol, phenol, cresol, xylol, phenylphenol, Examples include, but are not limited to, naphthol.

The metal compound (2) of the diethynylbenzene derivative is synthesized by various methods.
It is synthesized by reacting a diethynylbenzene derivative represented by the general formula (8) with an organometallic compound represented by the general formula (9).

[0038]

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[0039]

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In the formula, R ⁴ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and M ¹ represents a halide of an alkali metal or an alkaline earth metal.

The diethynylbenzene derivative (8) includes, for example, 1,4-diethynylbenzene, 1,3-diethynylbenzene, 1,2-diethynylbenzene, 2,5-diethynyltoluene, 5-diethynyltoluene, 2,5-diethynyl-
Examples include, but are not limited to, 1,4-xylene, 1,4-diethynyl-2-phenylbenzene, and the like.

Examples of the organometallic compound (9) include, but are not limited to, methyllithium, butyllithium, phenyllithium, and methylmagnesium bromide.

The organometallic compound (2) of the above-mentioned diethynylbenzene derivative can be reacted at an arbitrary molar ratio, but preferably, the diethynylbenzene derivative (8): the organometallic compound (9) = 1: 1 to 1 10 is preferred, and more preferably 1: 1.5-3. The reaction ratio between the above-mentioned diethynylbenzene derivative (8) and the organometallic compound (9) is too large to obtain the diethynylbenzene derivative metal compound (2) efficiently. Is limited to

In the above reaction, the solvent may be either polar or non-polar. Preferably, an aprotic solvent such as diethyl ether or tetrahydrofuran is used. The amount of the solvent used is, based on the diethynylbenzene derivative,
The concentration is 0.01 to 100 mol / L, preferably 0.1
〜１０10 mol / L.

The temperature of the reaction is not particularly limited, but is preferably between -78 ° C and the boiling point of the solvent, since the reaction rate is significantly lowered at -78 ° C or lower.

The above reaction time is preferably 1 to 48 hours regardless of whether the reaction time is short or long, since the yield of the resulting metal compound of the diethynylbenzene derivative is reduced.

The above reaction proceeds in an atmosphere of air or an inert gas. In order to increase the yield of the resulting metal compound of the diethynylbenzene derivative, the reaction is carried out in an atmosphere of an inert gas such as argon or nitrogen. It is preferable to do so.

The reaction of the metal compound (2) of the diethynylbenzene derivative with the halogenated silyl compound [(3) or (4)] is preferably carried out continuously after the preparation of the metal compound of the diethynylbenzene derivative. .

The metal compound of the diethynylbenzene derivative and the silyl halide compound can be reacted at an arbitrary molar ratio. Preferably, the metal compound of the diethynylbenzene derivative and the halogenated silyl compound = 1:
It is 0.01-100, more preferably 1: 0.1-10. The reaction ratio between the metal compound of the above-described diethynylbenzene derivative and the halogenated silyl compound is preferably within the above-mentioned range since a high molecular weight product cannot be obtained regardless of which one is higher.

The temperature of the above reaction is not particularly limited, but the reaction rate is remarkably lowered at -78 ° C or lower. Therefore, the reaction is preferably carried out at a temperature between -78 ° C and the boiling point of the solvent. The reaction time is preferably 1 to 48 hours since the yield of the obtained polymer is reduced whether it is short or long.

The above reaction proceeds under an atmosphere of an air or an inert gas, but it is preferable to carry out the reaction under an atmosphere of an inert gas such as argon or nitrogen in order to increase the yield of the obtained polymer.

After the above reaction, the reaction with the metal compound (5), water or alcohol is preferably carried out continuously. In the above reaction, a metal compound, water or an alcohol can be reacted at an arbitrary molar ratio in order to adjust the introduction amount of the side chain functional group, but the silyl halide compound used in the previous reaction: the metal compound, the water Or alcohol = 1: 0.01 to 1
00 is preferred, and more preferably 1: 0.1 to 10.

The temperature of the above reaction is not particularly limited, but the reaction rate is remarkably lowered at -78 ° C or lower. Therefore, the reaction is preferably carried out between -78 ° C and the boiling point of the solvent. The reaction time is preferably 1 to 48 hours since the yield of the obtained polymer is reduced whether it is short or long.
The above reaction proceeds in an atmosphere of air or an inert gas, but it is preferable to carry out the reaction in an atmosphere of an inert gas such as argon or nitrogen in order to increase the rate of introducing a functional group into a side chain.

Examples of a method for purifying the silicon-based polymer obtained by the above reaction include a reprecipitation method and fractionation by gel permeation chromatography.
Preferred is a reprecipitation method using a poor solvent such as water, methanol, ethanol, isopropanol, hexane, or petroleum ether, or a mixed solvent thereof.

Next, a method for producing the silicon-based polymer of the present invention 3 will be described. The present invention 3 is the production method of the present invention 1, wherein the halogenated arylene compound represented by the general formula (6) and the diethynylsilane compound represented by the general formula (7) are reacted in the presence of a transition metal catalyst. It is characterized by reacting.

[0056]

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[0057]

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In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, which may be the same or different, and X ² represents a halogen atom. Represent. The bonding position between R ¹ and the benzene ring is X
² is a carbon other than the substituted carbon. R ² represents an acetylene derivative group having 2 to 20 carbon atoms. R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an acetylene derivative group having 2 to 20 carbon atoms, and R ² and R ³ may be the same.

The above R ^{1 to} R ³ are limited to the above-mentioned range for the same reason as that of the first invention.
And the like.

The halogen atom represented by X ² includes bromine, iodine, chlorine and the like, and is preferably bromine or iodine.

Examples of the halogenated arylene compound (6) include, for example, 1,4-dibromobenzene, 1,3-dibromobenzene, 1,2-dibromobenzene, 2,5-dibromotoluene, 3,5-dibromotoluene , 2,5-dibromo-1,4-xylene, 1,4-dibromo-2-phenylbenzene and iodides, chlorides, fluorides and the like thereof, but are not limited thereto.

Examples of the diethynylsilane compound (7) include, for example, tetraethynylsilane, triethynylmethylsilane, triethynylethylsilane, triethynylpropylsilane, triethynylbutylsilane, triethynylphenylsilane, triethynyltolylsilane, Diethynyl (2-trimethylsilylethynyl) methylsilane, diethynyl (2-trimethylsilylethynyl) ethylsilane, diethynyl (2-trimethylsilylethynyl) propylsilane, diethynyl (2-trimethylsilylethynyl)
Butylsilane, diethynyl (2-trimethylsilylethynyl) phenylsilane, diethynyl (2-trimethylsilylethynyl) tolylsilane, diethynyl (2-phenylethynyl) methylsilane, diethynyl (2-phenylethynyl) ethylsilane, diethynyl (2-phenylethynyl)
Propylsilane, diethynyl (2-phenylethynyl) butylsilane, diethynyl (2-phenylethynyl) phenylsilane, diethynyl (2-phenylethynyl) tolylsilane, diethynyl (2-ethynylphenyl) methylsilane, diethynyl (2-ethynylphenyl) ethylsilane,
Diethynyl (2-ethynylphenyl) propylsilane, diethynyl (2-ethynylphenyl) butylsilane, diethynyl (2-ethynylphenyl) phenylsilane, diethynyl (2-ethynylphenyl) tolylsilane, diethynylvinylvinylsilane, diethynylvinylmethylsilane, Ethynylvinylethylsilane, diethynylvinylpropylsilane, diethynylvinylbutylsilane, diethynylphenylvinylsilane, diethynyltolylvinylsilane, diethynyldiallylsilane, diethynylallylmethylsilane, diethynylallylethylsilane, diethynylallylpropylsilane, Diethynyl allyl butyl silane, diethynyl phenyl allyl silane, diethynyl tolyl allyl silane, diethynyl hydroxymethyl silane, diethynyl hydroxyethyl silane Diethynylhydroxypropylsilane, diethynylhydroxybutylsilane, diethynylhydroxyphenylsilane, diethynylhydroxytolylsilane, diethynylmethoxymethylsilane, diethynylethoxymethylsilane, diethynylpropoxymethylsilane, diethynylbutoxymethylsilane, diethynyl Phenoxymethylsilane, diethynylmethoxyethylsilane, diethynylethoxyethylsilane, diethynylpropoxyethylsilane, diethynylbutoxyethylsilane, diethynylphenoxyethylsilane, diethynylmethoxypropylsilane, diethynylethoxypropylsilane, diethynylpropoxypropyl Silane, diethynylbutoxypropylsilane, diethynylphenoxypropylsilane, diethynylmethoxybuty Silane,
Diethynylethoxybutylsilane, diethynylpropoxybutylsilane, diethynylbutoxybutylsilane, diethynylphenoxybutylsilane, diethynylmethoxyphenylsilane, diethynylethoxyphenylsilane,
Diethynylpropoxyphenylsilane, diethynylbutoxyphenylsilane, diethynylphenoxyphenylsilane, diethynylmethoxytolylsilane, diethynylethoxytolylsilane, diethynylpropoxytolylsilane, diethynylbutoxytolylsilane, diethynylphenoxytolylsilane, and the like. But not limited to these.

As the transition metal catalyst, bis (triphenylphosphine) palladium dichloride ((PPh ₃ ) ₂ P
dCl ₂ ), tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ), and the like, but are not limited thereto.

When the amount of the transition metal catalyst used is small, the reactivity of polycondensation decreases, and when it is large, the transition metal catalyst tends to remain in the obtained polymer and deteriorates in physical properties. It is preferably 0.0001 to 1 times, more preferably 0.001 to 0.1 times.

Copper (I) iodide, triphenylphosphine and the like may be added as a promoter to the above transition metal catalyst.
Although the polycondensation reaction proceeds without adding such a cocatalyst, the addition of the cocatalyst can shorten the reaction time and improve the yield of the product.

The amount of the cocatalyst to be used is preferably from 0.001 to 1 times, more preferably from 0.01 to 0.1 times by mole based on the halogenated arylene compound (7). In addition to the above catalyst, an additive may be used to capture hydrogen halide generated in the reaction system. Such additives include, but are not limited to, triethylamine, diisopropylamine, and the like.

The above polycondensation reaction is preferably carried out in a solvent. The solvent may be either polar or non-polar. Preferably, an aprotic solvent such as tetrahydrofuran, diethyl ether, toluene and xylene is used. And particularly preferred are tetrahydrofuran and toluene.

The temperature of the above reaction is not particularly limited, but is preferably between -78 ° C. and the boiling point of the above solvent since the reaction rate is remarkably reduced below −78 ° C.

The above reaction proceeds under any atmosphere of an air or an inert gas, but is preferably performed under an atmosphere of an inert gas such as argon or nitrogen in order to increase the yield of the obtained polymer.

The above reaction time is preferably 1 to 48 hours since the yield of the obtained polymer is reduced whether it is short or long.

The method for purifying the silicon-based polymer obtained by the above polycondensation reaction includes, for example, a reprecipitation method and fractionation by gel permeation chromatography, and preferably water, methanol, ethanol, isopropanol. , Hexane, petroleum ether or the like, or a reprecipitation method using a mixed solvent thereof.

Next, the cured product of the silicon-based resin of the fourth invention will be described. The cured product of the silicon-based resin of the fourth invention is obtained by crosslinking the acetylene group or the functional group of the side chain in the main chain of the silicon-based polymer with heat, light or an electron beam. The obtained cured silicon-based resin exhibits excellent heat resistance and also improves mechanical strength and the like. Hereinafter, the crosslinking method will be described.

The heating temperature in the case of thermally cross-linking the above silicon-based polymer is too low, the cross-linking reaction does not sufficiently occur, so that the curing becomes insufficient. If the heating temperature is high, the silicon-based polymer deteriorates before cross-linking. The range is preferably from 500 to 500C, more preferably from 200 to 400C.

The thermal crosslinking reaction proceeds under an atmosphere of air or an inert gas or under reduced pressure, but preferably under an atmosphere of an inert gas such as nitrogen or argon or under reduced pressure. The reaction time of the thermal crosslinking reaction is preferably in the range of 1 minute to 10 hours, more preferably in the range of 30 minutes to 5 hours. Time range.

The photo-crosslinking of the silicon-based polymer is carried out by using ultraviolet light,
Irradiation with actinic rays of an electron beam is performed. In the case of irradiating ultraviolet rays, when the irradiation amount is small, the crosslinking reaction does not proceed sufficiently and curing is insufficient, and when the irradiation amount is large, a decomposition reaction occurs, so that the integrated exposure amount at 365 nm is 50 to 500.
0 mJ / cm ² is preferred.

As a light source used for the irradiation of the ultraviolet rays, for example, a high-pressure mercury lamp, a halogen lamp, a xenon lamp, a nitrogen laser, a He—Cd laser, an Ar laser, and the like are used.

When the silicon polymer is cross-linked by an electron beam, the irradiation amount of the electron beam is preferably 0.01 to 10 since the cross-linking reaction does not proceed sufficiently if the amount is too small, and the curing is insufficient. 100 Mrad is preferred.
The photocrosslinking reaction proceeds in an air or inert gas atmosphere, but is preferably in an inert gas atmosphere such as nitrogen or argon.

[0078]

Embodiments of the present invention will be described below. Example 1 After replacing the inside of a 200 mL three-necked flask with a 100 mL dropping funnel with argon, 2.52 g (20.0 mmol) of 1,4-diethynylbenzene and THF were added.
80 mL was charged, and the reaction system was cooled to -78 ° C. Subsequently, 25.0 mL of a 1.60 mol / L hexane solution of n-butyllithium was added dropwise over 15 minutes, and then -78.
The mixture was stirred at 1.5 ° C. for 1.5 hours to prepare 1,4-dilithioethynylbenzene. Separately from this, after replacing the inside of a 300 mL three-necked flask with a 200 mL dropping funnel with argon, 4.23 g of trichlorophenylsilane (20.0 m
mol) and THF (40 mL), the reaction system was cooled to 0 ° C, and THF of the prepared 1,4-dilithioethynylbenzene was added.
The suspension was added dropwise over 30 minutes. After the temperature was raised to room temperature and stirred for 16 hours, the mixture was further reacted for 8 hours while heating under reflux. Next, the mixture was cooled again to 0 ° C., 40.0 mL of a 0.50 mL ethynylmagnesium bromide THF solution was added dropwise over 15 minutes, and the mixture was stirred at 25 ° C. for 16 hours, and further heated under reflux.
Allowed to react for hours.

The reaction solution was dropped into a mixture of 50 mL of THF / 200 mL of an aqueous ammonium chloride solution.
Insolubles were removed by filtration, and the filtrate was extracted with THF. After drying the organic layer with anhydrous magnesium sulfate,
The drying agent was removed by filtration, and the solvent was distilled off until the volume became about 10 mL. The solution was dropped into 100 mL of methanol for reprecipitation, and the deposited precipitate was collected by filtration and dried under reduced pressure to obtain 597 mg of a pale yellow solid.

FIG. 1 shows the results of measuring the IR spectrum (using "FTS135 system" manufactured by Bio-Rad) of the above product. As shown in FIG. 1, C-H stretching vibration 3278cm ^-1 terminal acetylene group, C [identical to] C stretching vibration of terminal acetylene groups to 2044cm ^-1, C≡C stretching vibration of an internal acetylene group to 2161cm ^-1, 1430, 1116
At cm ⁻¹ , absorption based on the bending vibration of the Si—Ph group was observed.

Further, the ¹ H-NMR spectrum (using DRX300 manufactured by Bruker) of the above product was measured (FIG. 2). The proton of the terminal acetylene group was found to be 3.30 ppm, and 7.38 to 7.95 ppm. A peak based on the proton of the phenyl group was confirmed. Further, the GPC (manufactured by JASCO Corporation) of the above product was measured, and as a result, the weight average molecular weight was 28,500 in terms of polystyrene. From the above, the product was identified as a silicon-based polymer having a functional group in a side chain having a structural unit represented by the general formula (10) (where Ph represents a phenyl group) as a constituent unit. (Yield 11%).

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The above silicon-based polymer was treated under a nitrogen atmosphere with 3
It was heated at 00 ° C. for 2 hours to obtain a cured silicon-based resin.

(Example 2) After replacing the inside of a 100 mL two-necked flask with a reflux condenser with argon, 901 mg (5.00 mmol) of triethynylphenylsilane, 1,1,
1.18 g (5.00 mmol) of 4-dibromobenzene
, Toluene 20 mL, bis (triphenylphosphine)
35 mg (0.05 mmol) of palladium dichloride
, 19 mg (0.05 mmol) of copper iodide, 26 mg (0.05 mmol) of triphenylphosphine, and 2.02 (20.0 mmol) of diisopropylamine, and the reaction system was refluxed for 16 hours.

Next, the reaction solution was added dropwise to a mixture of 50 mL of THF / 200 mL of an aqueous ammonium chloride solution, insolubles were removed by filtration, and the filtrate was extracted with THF. After the organic layer was dried over anhydrous magnesium sulfate, the desiccant was removed by filtration, and the solvent was distilled off until the volume became about 10 mL. The solution was re-precipitated by dropping it into 100 mL of methanol, and the deposited precipitate was collected by filtration and dried under reduced pressure.
73 mg of a dark brown solid were obtained.

FIG. 3 shows the results of measuring the IR spectrum of the above product (using an FTS135 system manufactured by Bio-Rad). As shown in FIG. 3, C-H stretching vibration of terminal acetylene groups to 3283cm ^-1, C≡C stretching vibration of terminal acetylene groups to 2039cm ^-1, C≡C stretching vibration of an internal acetylene group to 2158cm ^-1, 1429 , 1121
At cm ⁻¹ , absorption based on the bending vibration of the Si—Ph group was observed. Further, the GPC (manufactured by JASCO Corporation) of the above product was measured, and as a result, the weight average molecular weight was 24,
600.

From the above, the product was represented by the general formula (10)
Was identified as a side chain functional group-containing silicon-based polymer having a structure represented by a structural unit (yield: 6%). The silicon-based polymer is heated at 300 ° C. for 2 hours under a nitrogen atmosphere,
A silicon-based resin cured product was obtained.

(Comparative Example 1) The inside of a 100 mL two-necked flask equipped with a reflux condenser was replaced with argon, 504 mg (4.00 mmol) of 1,4-diethynylbenzene and 20 mL of tetrahydrofuran were added, and the reaction system was cooled to -78 ° C. After that, 5.00 mL of a 1.6 mL n-butyllithium hexane solution was added over 2 minutes. Subsequently, the temperature was raised to 20 ° C., and the mixture was stirred for 16 hours. After cooling to −78 ° C. again, 1.01 g of diphenyldichlorosilane (4.00 m
mol) in THF (2 mL).
The mixture was heated under reflux for 2 hours.

After adding ion-exchanged water to stop the reaction,
The mixture was extracted with THF, and the organic layer was dried over anhydrous magnesium sulfate. After removing the drying agent by filtration, the solvent was distilled off under reduced pressure to obtain a yellow-brown solid. 3 m of this product
As a result of dissolving in L of THF and dropping into 50 mL of methanol for reprecipitation, 809 mg of a pale yellow-brown solid was obtained.

As a result of measuring the IR spectrum of the above product (using “270-30” manufactured by Hitachi, Ltd.), 2160c
The absorption based on the acetylene bond is found at m ⁻¹ as 1420, 11
At 20 cm ⁻¹ , absorption based on a Si—Ph bond was observed. The ¹ H-NMR spectrum of the above product (using “R-9000” manufactured by Hitachi, Ltd.) was measured. As a result, a peak based on a phenyl group was found at 7.45 to 7.85 ppm. Further, the weight average molecular weight of the above product was measured (using GPC manufactured by JASCO Corporation). As a result, it was 4,000 in terms of polystyrene.

From the above, the product is represented by the general formula (11)
(A yield of 66%). The silicon-based polymer was heated at 300 ° C. for 2 hours in a nitrogen atmosphere to obtain a cured silicon-based resin.

[0092]

Embedded image

The silicon-based polymers obtained in the above Examples and Comparative Examples were subjected to thermogravimetric analysis (“SSC
5200 System ”) under nitrogen atmosphere.
The temperature is raised from 30 ° C. to 800 ° C. at a rate of 0 ° C./min,
5 wt% relative to the initial weight and 10% by weight reduced temperature when (hereinafter referred to as Td ₅ and Td ₁₀₎ and 800
The residual weight ratio (hereinafter referred to as W ₈₀₀ ) at ℃ is measured,
Table 1 shows the results of evaluating the heat resistance.

[0094]

[Table 1]

As is clear from Table 1, the silicon-based polymer having a functional group in the side chain obtained according to the present invention has higher heat resistance than a conventional polymer having no functional group. Was. It was also found that the heat resistance was improved by the crosslinking reaction.

Further, the same heat resistance was evaluated for the cured silicon-based resin of Example in an air atmosphere, and the results are shown in Table 2.

[0097]

[Table 2]

[0098]

Industrial Applicability The silicon-based polymer of the present invention 1 and the present invention 4
The cured silicon-based resin has excellent heat resistance as described above, and is suitably used for aerospace and aviation materials. According to the production methods of the present invention 2 and the present invention 3, the silicon-based polymer can be produced relatively easily.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of the silicon-based polymer obtained in Example 1.

FIG. 2 shows ¹ H—N of the silicon-based polymer obtained in Example 1.
It is an MR spectrum.

FIG. 3 is an IR spectrum of the silicon-based polymer obtained in Example 2.

FIG. 4 is an IR spectrum of the silicon-based polymer (upper figure) and the cured silicon-based resin (lower figure) obtained in Example 1.

FIG. 5 is an IR spectrum of a silicon-based polymer (upper figure) and a cured silicon-based resin (lower figure) obtained in Example 2.

Claims (4)

[Claims] 1. A silicon-based polymer having a structure represented by the general formula (1) as a constituent unit and having a weight average molecular weight of 500 or more. Embedded image (Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, which may be the same or different, and a bond between R ¹ and a benzene ring The position is a carbon other than the carbon substituted by the ethynyl group, R ² is an acetylene derivative group having 2 to 20 carbon atoms, R ³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, An aryl group having 6 to 30 carbon atoms or an acetylene derivative group having 2 to 20 carbon atoms, wherein R ² and R ³ may be the same. 2. After reacting a metal compound of a diethynylbenzene derivative represented by the general formula (2) with a silyl halide compound represented by the general formula (3) or (4), The method for producing a silicon-based polymer according to claim 1, wherein the reaction is performed with at least one of a metal compound represented by the formula (5), water, and an alcohol. Embedded image Embedded image Embedded image Embedded image (Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, which may be the same or different, and a bond between R ¹ and a benzene ring R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an acetylene derivative having 2 to 20 carbon atoms. X ¹ represents a halogen atom, R ² represents an acetylene derivative group having 2 to 20 carbon atoms, R ² and R ³ may be the same, and M ¹ and M ² are
Shows alkali metal or alkaline earth metal halide) 3. The method according to claim 1, wherein the halogenated arylene compound represented by the general formula (6) and the diethynylsilane compound represented by the general formula (7) are reacted in the presence of a transition metal catalyst. 2. The method for producing a silicon-based polymer according to 1. Embedded image Embedded image (In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, which may be the same or different, and X ² represents a halogen atom. The bonding position between R ¹ and the benzene ring is a carbon other than the carbon substituted by X ^2. R ² has 2 to 20 carbon atoms.
Is an acetylene derivative group. R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group or an acetylene derivative group having 2 to 20 carbon atoms having from 6 to 30 carbon atoms, R ²
And R ³ may be the same) 4. A silicon-based resin cured product obtained by crosslinking the silicon-based polymer according to claim 1.