JPH07309952A - Polysilane derivative having anthrylene group in part of main chain and its production - Google Patents

Abstract

(57) [Summary] [Object] To provide a high molecular weight organosilicon polymer which emits light in the visible region, has excellent luminous efficiency, and is soluble in common organic solvents, and a method for producing the same. ## STR1 ## Formula A: (In the formula, R ¹ and R ² are the same or different and have 1 to 6 carbon atoms.
And a structural unit A represented by the formula B, in which the total number of carbon atoms of R ¹ and R ² is 8 or less. (In the formula, R ³ and R ⁴ may be the same or different and are an alkyl group, an aryl group or an aralkyl group having 1 to 10 carbon atoms). A polysilane derivative having an anthrylene group in a part of the main chain, wherein the molar ratio (%) of A / structural unit B is 0.5 to 10% and the weight average molecular weight is 1,000 to 1,000,000.
And its manufacturing method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organosilicon polymer useful as a light emitting material, a photoconductive material, a resist material and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Organosilicon-based polymers have recently attracted attention as polymers having a light emitting function and the like. For example, it has been clarified that organic polysilane emits light by σ-σ conjugation derived from the Si—Si bond of the main chain. For example, a typical polysilane, poly (methyl-n-propylsilane), exhibits an emission spectrum having a maximum wavelength of 340 nm, and poly (di-n-hexylsilane) has 342.
It shows light emission with a maximum wavelength of nm. However, since the emission wavelength of the polysilane is in the ultraviolet region, it cannot be applied as a material for a display element or the like. On the other hand, in poly (diphenylsilane) in which two substituents are all aryl groups, poly (diphenylsilane) soluble in an organic solvent, in which an alkyl group is introduced into the para-position of both phenyl groups located in the side chains thereof, -P-alkylphenylsilane) is known to have an emission maximum near the visible region of 400 nm [Chemic Reviews (Chemic
al Reviews), Vol. 89, No. 6, 1382 (198).
9 years)]]. However, the luminous efficiency is considerably low, and in order to obtain a poly (di-p-alkylphenylsilane) soluble in an organic solvent, the alkyl group has a relatively long chain n-butyl or n-hexyl group. It was necessary to introduce. This makes it very difficult to synthesize the raw material monomers for obtaining the polymer, and
The reactivity of the monomer was lowered, and the resulting polymer was obtained only in a yield of about several%, which was not satisfactory in practical use together with the low emission efficiency. Further, as a publication relating to an organosilicon-based polymer, the formula

[0003]

[Chemical 5]

(In the formula, R ^a represents a π-conjugated divalent organic group having 2 to 30 carbon atoms, R ^b represents a hydrocarbon group having 1 to 30 carbon atoms, and X ^a represents ^a halogen atom. , M is 1 ≦ m ≦
JP-A-6-9786 discloses ^a silicon-containing organic compound represented by the formula (2, n represents a number satisfying n ≧ 2) (arylene group is included in various groups listed as ^Ra ). Also, in the description of the prior art in this publication, a poly (disilanine phenylene) derivative, a poly (disilanylene naphthylene) derivative and the like are mentioned. Regarding the monomer, the formula

[0005]

[Chemical 6]

A compound represented by the following formula is known (The 68th Annual Meeting of the Chemical Society of Japan, Proc. 353 (1994)).

[0007]

DISCLOSURE OF THE INVENTION The present inventors have earnestly studied for the purpose of obtaining a high molecular weight organosilicon polymer which emits light in the visible region, has excellent luminous efficiency, and is soluble in ordinary organic solvents. As a result, they have found a polymer that meets such an object and completed the present invention.

[0008]

The present invention provides the formula A

[0009]

[Chemical 7]

(In the formula, R ¹ and R ² are the same or different linear alkyl groups having 1 to 6 carbon atoms, and R ¹ and R ^{2 are}
The total number of carbon atoms of is 8 or less)
And formula B

[0011]

[Chemical 8]

(Wherein R ³ and R ⁴ may be the same or different and are an alkyl group, an aryl group or an aralkyl group having 1 to 10 carbon atoms). , The molar ratio (%) of structural unit A / structural unit B is 0.5 to 1
The present invention relates to a polysilane derivative having 0% and a weight average molecular weight of 1,000 to 1,000,000 and containing an anthrylene group in a part of its main chain, and a method for producing the same.

In the structural unit A which is one structural unit of the polysilane derivative of the present invention, R ¹ and R ² are the same or different linear alkyl groups having 1 to 6 carbon atoms, and
The total carbon number of R ¹ and R ² is 8 or less. Preferred R ¹ or R ² is a linear alkyl group having 1 to 4 carbon atoms,
Further more preferably, one of R ¹ and R ² is a methyl group. If R ¹ or R ² is branched, the carbon number of R ¹ or R ² exceeds 6, or the total number of carbon atoms of R ¹ and R ² exceeds 8, the steric hindrance will cause a later-mentioned occurrence. The reactivity of the compound represented by the formula [1] and the compound represented by the formula [2], which are the raw materials, in the presence of an alkali metal or an alkaline earth metal is decreased, and the yield of the polysilane derivative of the present invention is reduced. It leads to deterioration and is industrially disadvantageous. R ¹ and
Specific examples of R ² include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and an n-hexyl group.

In the structural unit B which is the other structural unit of the polysilane derivative of the present invention, R ³ and R ⁴ may be the same or different, and a linear or branched alkyl group having 1 to 10 carbon atoms. A group, an aryl group or an aralkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, specifically, a methyl group,
n-propyl group, i-propyl group, n-butyl group, se
Examples thereof include c-butyl group. Moreover, a methylene group, an ethylene group, etc. are mentioned as an alkylene group in the said aralkyl group. Further, in the present invention, the aryl group and the aralkyl group may be a silane compound represented by the formula [2] and a substituent that does not react with an alkali metal or an alkaline earth metal during the later-described polymerization for producing the polysilane derivative. Those having on the ring are also included, and examples of such a substituent include a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (eg, methyl group, ethyl group, n-propyl group). , I-propyl group, etc.),
Examples thereof include linear or branched alkoxy groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, etc.). Specific examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group,
Examples thereof include a methoxyphenyl group, an ethoxyphenyl group and a naphthyl group. Further, as the aralkyl group, specifically, a benzyl group, a tolylmethyl group, a xylylmethyl group, a cumenylmethyl group, a phenethyl group, a diphenylmethyl group,
Examples thereof include trityl group, tritolylmethyl group, tri (dimethylphenyl) methyl group, methoxyphenylmethyl group, diethoxyphenylmethyl group and the like.

The combination of R ³ and R ⁴ is not particularly limited, but any one of them has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.
Is a linear or branched alkyl group, especially a methyl group,
The other is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms, an aryl group or an aralkyl group. A particularly preferred combination of R ³ and R ^{4 is} a combination of a methyl group on one side and a linear alkyl group or aryl group having 1 to 4 carbon atoms on the other side.

The molar ratio (%) of structural unit A / structural unit B constituting the polysilane derivative of the present invention is 0.5 to 10%. When the molar ratio (%) is less than 0.5%, the proportion of anthrylene group becomes too small, and light emission in the visible region does not occur or is too weak, and the light emission efficiency becomes poor. 10% again
If it is larger, the number of repeating structural units B is insufficient, and the function as polysilane, for example, energy band and hole (hole) transportability cannot be obtained. In order for the polysilane part to form a sufficient energy band (σ-σ band) and to have a hole transporting property and to be conjugated with the π electron of the anthrylene part, the molar ratio (%) must be 5% or less. Is preferable, and in order to obtain a sufficient function of visible light emission, the molar ratio (%) is preferably 1% or more. In addition, the said molar ratio (%) means the molar ratio (%) calculated | required by the method mentioned later.

The weight average molecular weight of the polysilane derivative of the present invention is 1,000 to 1,000,000, preferably 2,000 to 500,000.
Is. If the weight average molecular weight is less than 1,000, it will be difficult to isolate and purify the polymer, and the produced polymer will be difficult to mold and process.If it exceeds 1,000,000, it will be too viscous if dissolved in a solvent. However, the film forming performance by spin coating, casting method, etc. becomes poor. In addition, the said weight average molecular weight means the weight average molecular weight calculated | required by GPC method (polystyrene conversion). The polysilane derivative of the present invention is soluble in various organic solvents, especially aprotic organic solvents such as benzene, toluene, xylene, n-hexane, n-octane and tetrahydrofuran. The polysilane derivative of the present invention has the formula [1]

[0018]

[Chemical 9]

(In the formula, R ¹ and R ² are the same or different linear alkyl groups having 1 to 6 carbon atoms, and R ¹ and R ^{2 are}
Has a total carbon number of 8 or less, and X ¹ and X ² are the same or different halogen atoms) 9,10-
Bis (dialkylhalosilyl) anthracene (hereinafter referred to as bissilylanthracene compound [1]) and a compound of formula [2]

[0020]

[Chemical 10]

(In the formula, R ³ and R ⁴ may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, an aryl group or an aral group, and X ³ and X ⁴ are the same or different. And a silane compound represented by different halogen atoms) (hereinafter referred to as silane compound [2]) in the presence of an alkali metal or an alkaline earth metal in an inert solvent. it can. The bissilylanthracene compound [1] is a novel compound, and its production method will be described later. R ^{1 of} bissilylanthracene compound [1]
And R ² are as described for the polysilane derivative of the present invention. The halogen atom represented by X ¹ or X ² is preferably a chlorine atom or a bromine atom,
Particularly preferred is a chlorine atom.

Preferred examples of the bissilylanthracene compound [1] include 9,10-bis (dimethylchlorosilyl) anthracene, 9,10-bis (diethylchlorosilyl) anthracene and 9,10bis (di-n-propylchlorosilyl). ) Anthracene, 9,10-bis (di-n-butylchlorosilyl) anthracene, 9,10-bis (methylethylchlorosilyl) anthracene, 9,10-bis (methyl n-propylchlorosilyl) anthracene,
9,10-bis (methyl n-butylchlorosilyl) anthracene, 9,10-bis (methyl n-pentylchlorosilyl) anthracene, 9,10-bis (methyl n-hexylchlorosilyl) anthracene, 9,10-bis (Ethyl n-propylchlorosilyl) anthracene,
9,10-bis (ethyl n-butylchlorosilyl) anthracene, 9,10-bis (ethyl n-pentylchlorosilyl) anthracene, 9,10-bis (ethyl n-hexylchlorosilyl) anthracene, 9,10-bis (N-propyl n-butylchlorosilyl) anthracene and 9,10-bis (n-propyl n-pentylchlorosilyl) anthracene are mentioned, and particularly preferred examples are 9,10-bis (dimethylchlorosilyl) anthracene and 9 , 10-bis (methylethylchlorosilyl) anthracene, 9,10-bis (methyl n-propylchlorosilyl) anthracene, 9,10-bis (methyl n-)
Butylchlorosilyl) anthracene, 9,10-bis (methyl n-pentylchlorosilyl) anthracene,
Mention may be made of 9,10-bis (methyl n-hexylchlorosilyl) anthracene.

R ³ and R ⁴ of the silane compound [2] are as described for the polysilane derivative of the present invention. See also X ³
Alternatively, the halogen atom represented by X ⁴ is preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom. Preferred examples of the silane compound [2] include dimethyldichlorolane, diethyldichlorosilane, dipropyldichlorosilane, dibutyldichlorosilane, dipentyldichlorosilane, dihexyldichlorosilane, methylethyldichlorosilane, methylpropyldichlorosilane, methylbutyldichlorosilane, Methylpentyldichlorosilane, methylhexyldichlorosilane, ethylpropyldichlorosilane, ethylbutyldichlorosilane, ethylpentyldichlorosilane, ethylhexyldichlorosilane, propylbutyldichlorosilane, methylphenyldichlorosilane, ethylphenyldichlorosilane, methyltolyldichlorosilane, ethyl Tolyldichlorosilane, methylxylyldichlorosilane, ethylxylyldichlorosilane, methylnaphthyl Dichlorosilane,
Examples thereof include methylpentyldichlorosilane, ethylbenzyldichlorosilane, and methylphenethyldichlorosilane. Particularly preferred examples are dimethyldichlorosilane, methylethyldichlorosilane, methyl n-propyldichlorosilane, methyl n-butyldichlorosilane, and methylphenyldichlorosilane. Examples include chlorosilane and the like. The polysilane derivative of the present invention is the bissilylanthracene compound [1].
And the above silane compound [2] are obtained by reacting in the presence of an alkali metal or an alkaline earth metal, particularly preferably an alkali metal, in an inert solvent. The alkali metal may be lithium, sodium or potassium. And the like, lithium and sodium are preferable,
Sodium is particularly preferred. Examples of the alkaline earth metal include magnesium and calcium.

Since the optimum ratio of the bissilylanthracene compound [1] and the silane compound [2] used as the raw materials differs depending on the reactivity of the two raw materials, the molar ratio of structural unit A / structural unit B of the target polysilane derivative. It is desirable to confirm the required amount experimentally after setting (%) before use. The proportion of alkali metal or alkaline earth metal used is 2 to 5 based on 1 mol of the total amount of the bissilylanthracene compound [1] and the silane compound [2].
Molar is preferred. If it is less than 2 moles, the yield of the reaction product is reduced, and if it exceeds 5 moles, the corresponding effect cannot be expected and it is uneconomical, and the amount of excess alkali metal or alkaline earth metal increases. , Then the processing becomes difficult. An aprotic solvent is suitable as the inert solvent, and specific examples thereof include benzene, toluene, xylene, n-hexane, n-octane, and tetrahydrofuran. The inert solvent is preferably used so that the concentration of the silane compound [2] is 100 mmol / L to 1 mol / L.

The reaction temperature is preferably 0 ° C. or higher and not higher than the boiling point of the reaction solvent. The reaction is preferably carried out under an inert gas atmosphere. The reaction time varies depending on the reaction solvent used and the reaction temperature, but the reaction is usually completed within 24 hours.
After completion of the reaction, the reaction solution is filtered to remove the by-product metal salt, and the filtrate is dropped into a poor solvent such as methanol to precipitate the product, whereby the target polysilane derivative can be obtained. The bissilylanthracene compound [1], which is one of the raw materials for producing the above-mentioned polymer, is also a novel compound, for example, a compound of the formula [3]

[0026]

[Chemical 11]

9,10-dilithioanthracene represented by the formula or the formula [4]

[0028]

[Chemical 12]

A Grignard reagent represented by the formula: wherein X ⁵ is a halogen atom, that is, 9,10-dimagnesium halogenoanthracene, and a compound of the formula [5]

[0030]

[Chemical 13]

(In the formula, R ¹ and R ² are the same as defined above, and X ⁶
Is the same as X ¹ or X ² of the compound [1]) and is easily obtained in high yield by reacting with a dialkyldihalosilane represented by the formula [1] in an inert solvent in an inert gas atmosphere. be able to. The halogen atom represented by X ⁵ is preferably a chlorine atom or a bromine atom. The halogen atom represented by X ⁶ is preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom. An aprotic organic solvent is suitable as the inert solvent, and specific examples thereof include diethyl ether, tetrahydrofuran, n-hexane, n-octane, and n-octane.
Pentane, benzene, toluene, xylene and the like can be mentioned. Examples of the inert gas include argon and nitrogen. The inert solvent is preferably used in such an amount that the concentration of 9,10-dilithioanthracene [3] or 9,10-dimagnesium halogenoanthracene [4] is 100 mmol / L to 2 mol / L. Dialkyldihalosilane [5]
And 9,10-dilithioanthracene [3] or 9,1
The reaction ratio with 0-dimagnesium halogenoanthracene [4] is 9,10-dilithioanthracene [3] or 9,10-dimagnesium halogenoanthracene [4] with dialkyldihalosilane [5] being 2 to 1
It is preferably 0 equivalent, and more preferably 2 to 6 equivalents. The reaction temperature is preferably -30 to 70 ° C, more preferably 0 to 50 ° C, most preferably 10 to 50 ° C. If the reaction temperature is too low, the yield of the bissilylanthracene compound [1] may decrease. The reaction time varies depending on the reaction temperature, the reaction solvent and the like, but the reaction is usually completed within 24 hours.

[0032] When obtaining the X ¹ and X ² are different bis silyl anthracene compound [1] above, for example, X ⁶ and dialkyldihalosilane (5) X ⁶ is X ¹ is a X ² Means such as using a mixture of dialkyldihalosilanes [5] or sequentially reacting both compounds with 9,10-dilithioanthracene [3] or 9,10-dimagnesium halogenoanthracene [4] at different times can be used. Can be taken. To obtain the produced bissilylanthracene compound [1] from the reaction solution obtained by the above reaction, the by-produced lithium halide or magnesium halide precipitate is removed from the reaction solution by filtration, decantation or the like, and then the reaction solvent is used. May be distilled off under reduced pressure, and the residue may be purified by a method such as recrystallization from an inert solvent such as pentane. The obtained bissilylanthracene compound [1] is a yellow solid. The bissilylanthracene compound [1] does not have to be purified for the next polymerization, and may be subjected to the polymerization at a stage after the reaction solvent is distilled off under reduced pressure.

Further, dialkyldihalosilane [5] used for the production of bissilylanthracene compound [1]
And the silane compound [2] that reacts with the produced bissilylanthracene compound [1] are the same compound, when the bissilylanthracene compound [1] is produced,
One reaction can be achieved by using an alkali metal or alkaline earth metal in the presence of dialkyldihalosilane [5] in a sufficient amount not only for the production of the bissilylanthracene compound [1] but also for the production of the next polymer. The polysilane derivative of the present invention can be obtained in the system.

[0034]

EXAMPLES The present invention will be specifically described below based on Reference Examples and Examples. In the examples, the weight average molecular weight and the number average molecular weight were determined by the GPC method (in terms of polystyrene), and the molar ratio (%) of structural units and the luminous efficiency were determined by the methods described below. (1) Molar ratio (%) of structural units It is calculated by the following procedure. The standard absorbance for anthracene is determined as follows. A standard solution in which a predetermined molar amount of anthracene is dissolved in a chloroform solvent is prepared, and the molar absorbance at λmax of UV absorption is measured, and this is used as the standard absorbance. The number of moles of structural unit A in the desired product is determined as follows. Target product (polymer) with the same solvent as the standard solution and the same molar concentration (converted from the number average molecular weight of the entire polymer)
A solution is prepared, and the molar absorptivity of λmax attributed to anthracene in UV absorption is measured and divided by the standard absorbance described above to obtain the number of moles of the anthrylene group in the target product. This value is equal to the number of moles of structural unit A.

The weight of the structural unit A in the desired product is calculated by the following formula. Weight of structural unit A = (molecular weight of structural unit A obtained by subtracting halogen atoms X ¹ and X ² from bissilylanthracene compound [1] used as a raw material) x (mol number of structural unit A) Structure in target product The number of moles of unit B is calculated by the following formula. Number of moles of structural unit B = (weight of target product used for measurement of molar absorbance−weight of structural unit A) / (structure obtained by subtracting halogen atoms X ³ and X ⁴ from silane compound [2] used as a raw material Molecular Weight of Unit B) The molar ratio (%) of structural unit A / structural unit B in the target product is calculated by the following formula. Structural unit A / structural unit B [molar ratio (%)] = (number of moles of structural unit A determined by) × 100 / (number of moles of structural unit B determined by) (2) Luminous efficiency Standard substance in chloroform As the formula

[0036]

[Chemical 14]

The measurement was performed using Alq ₃ represented by (Emission efficiency: 10.1%). Reference Example 1 In a reactor equipped with a stirrer and an external cooling jacket, 9,10-
Dibromoanthracene (2.11 g, mmol) was added thereto, and the system was degassed in vacuum and then put in a dry argon atmosphere. Add 30 ml of dehydrated and purified diethyl ether and add n-butyllithium (1.
0 g) of hexane (9.8 ml) was gradually fed to the reactor,
Stir for 3 hours at 10 to 30 ° C under an argon atmosphere,
The 9,10-dilithioanthracene was prepared. In a separate reactor equipped with stirrer and external cooling jacket, 10 ml of diethyl ether and 4.0 g of dimethyldichlorosilane (31 mmo)
l) was added, and the 9,10-dilithioanthracene-containing reaction mixture obtained above was added dropwise to the contents at room temperature under an argon atmosphere and stirred at 10 to 30 ° C. for 20 hours for reaction. By-produced lithium chloride was filtered off, the reaction solvent was distilled off under reduced pressure, and then recrystallized from n-pentane to obtain 9,10-bis (dimethylchlorosilyl) anthracene as a yellow solid. The yield was 70%.

As a result of analyzing the chlorine content of this compound,
The chlorine content is 19.40% by weight, calculated as 19.
It was in good agreement with 51% by weight. The infrared absorption spectrum (by the KBr method) of this compound was measured and found to be 125
Absorption was shown at 0.1440 cm ^-1 (Si-CH ₃ ). Also, ¹
The H nuclear magnetic resonance spectrum (measured using deuterated chloroform (7.25 ppm) as a standard) is shown in FIG. From FIG. 1, the chemical shift δ (ppm) is 8.5 to 7.4 (9,10-substituted anthracene), 0.7 (Si-CH ₃ ), and the result measured by MS spectrum shows m / z. 362 (M ⁺ ), and the obtained compound is 9,10-bis (dimethylchlorosilyl)
It indicates that it is anthracene.

Reference Example 2 A reactor equipped with a stirrer and an external cooling jacket was charged with 10 ml of diethyl ether and 5.0 g (32 mmol) of methyl n-propyldichlorosilane, and the mixture was heated to 10 to 3 under an argon atmosphere.
9,1 manufactured by the same operation as in Example 1 at 0 ° C
0-Dilithioanthracene was added dropwise to the contents. After completion of dropping, the reaction was completed by stirring at room temperature for 20 hours, by-produced lithium chloride was filtered off, the reaction solvent was distilled off under reduced pressure, and then recrystallized from n-pentane,
9,10-Bis (methyl n-propylchlorosilyl) anthracene was obtained as a yellow solid. The yield was 65%. As a result of analyzing the chlorine content of this compound, the chlorine content was 16.54% by weight, which was in good agreement with the calculated value of 16.90% by weight. Also, the ¹ H nuclear magnetic resonance spectrum of this compound
(Measured using deuterated chloroform (7.25 ppm) as a standard) is shown in FIG. From Figure 2, the chemical shift δ (ppm) is 8.5-
7.5 (9,10-substituted _{anthracene), 1.54 (-Si-CH 2} -CH 2
-), 1.09 (-Si-CH ₃ ), 1.03 (-CH ₂ -CH ₂ -C H ₃ ), and the result of measurement by MS spectrum was m / z 418 (M ⁺ ), which was the obtained compound. Is 9,10-bis (methyl n-propylchlorosilyl) anthracene.

Example 1 Combination of methyl n-propyl polysilane containing an anthrylene group
Sodium container 500ml in adult argon atmosphere 4.6
g and 160 ml of toluene were charged. Next, the system was heated to the boiling point of toluene, sodium was melted in a reflux atmosphere, and the mixture was vigorously stirred to finely disperse sodium. Then keep the content temperature near the boiling point of the solvent while stirring,
A mixture of 3 mmol (1.26 g) of 9,10-bis (methyl n-propylchlorosilyl) anthracene obtained in Reference Example 2 and a 20-fold molar amount of methyl n-propyldichlorosilane (9.42 g) was gradually added dropwise. did. After the dropping was completed, the reaction was carried out for about 3 hours near the boiling point of the solvent. After completion of the polymerization reaction, the mixture was cooled to room temperature, sodium chloride produced as a by-product and excess sodium metal were separated by filtration, and the filtrate was added dropwise to methanol to precipitate the polymer. By separating the precipitated polymer and drying it, a structural unit A in which R ¹ = methyl group, R ² = n-propyl group and a structural unit B in which R ³ = methyl group, R ⁴ = n-propyl group are formed. Target polymer 2.12 g
(Yield 34.2%) was obtained as a yellow solid. This polymer showed a bimodal molecular weight distribution consisting of components having a weight average molecular weight (Mw) of 335,000 and 9,600 (Fig. 3). The number average molecular weight (Mn) of the whole polymer was 4,500, and the molar ratio (%) of structural unit A / structural unit B of the present polymer was 1.5%. The emission spectrum of this polymer showed emission at 455 nm.

Example 2 Synthesis of methylphenylpolysilane containing anthrylene group Methylphenyldichlorosilane instead of methyl n-propyldichlorosilane and 9,1 obtained in Reference Example 2
R ¹ was prepared using 0-bis (methyl n-propylchlorosilyl) anthracene in the same amount, conditions and procedure as in Example ^1.
= Methyl group, R ² = n-propyl group, structural units A and R ³
= A methyl group and R ⁴ = a phenyl group, a yellow polymer composed of the structural unit B was synthesized. Polymer yield is 3.94g
(Yield 47.8%). This polymer has Mw of 415,0
A bimodal molecular weight distribution consisting of 00 and 6,200 components is shown (Fig. 4). The Mn of the whole polymer was 3,500, and the molar ratio (%) of structural unit A / structural unit B of the present polymer was 3.5%. The emission spectrum of this polymer showed emission at 480 nm. Furthermore, the luminous efficiency of this polymer was 15%, which was 1.5 times that of Alq ₃ .

[0042]

Industrial Applicability Since the polysilane derivative of the present invention has a light emission wavelength in the visible region and has a high light emission efficiency, it can be applied as an electronic material for display devices and the like, and is preferably an organic solvent, preferably an aproton. Organic solvents, especially benzene,
Since it is soluble in non-polar aromatic solvents such as toluene and xylene, it is easy to form into a film and therefore easy to form into an electronic material, and it is convenient for measuring the physical properties of the polymer itself, and since it is a polymer, the film Can be molded into Therefore, the polysilane derivative of the present invention can be used as a light emitting material, a photoconductor, a photoresist, an optical memory material, and the like.

[Brief description of drawings]

FIG. 1 shows a ¹ H nuclear magnetic resonance spectrum of 9,10-bis (dimethylchlorosilyl) anthracene of Reference Example 1.

FIG. 2 shows a ¹ H nuclear magnetic resonance spectrum of 9,10-bis (methyl n-propylchlorosilyl) anthracene of Reference Example 2.

FIG. 3 shows the molecular weight distribution of the polymer obtained in Example 1.

FIG. 4 shows the molecular weight distribution of the polymer obtained in Example 2.

Claims (2)

[Claims] 1. The formula A: (In the formula, R ¹ and R ² are the same or different and have 1 to 6 carbon atoms.
And a structural unit A represented by the formula B, in which the total number of carbon atoms of R ¹ and R ² is 8 or less. (In the formula, R ³ and R ⁴ may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group.) A polysilane derivative having an anthrylene group in a part of its main chain, which has a molar ratio (%) of A / structural unit B of 0.5 to 10% and a weight average molecular weight of 1,000 to 1,000,000. 2. A formula [1]: (In the formula, R ¹ and R ² are the same or different and have 1 to 6 carbon atoms.
Is a straight-chain alkyl group, and the total number of carbon atoms of R ¹ and R ² is 8 or less, and X ¹ and X ² are the same or different halogen atoms). (Dialkylhalosilyl) anthracene and a compound of the formula [2] (In the formula, R ³ and R ⁴ may be the same or different and are an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, and X ³ and X ⁴ are the same or different halogen atoms. The method for producing a polysilane derivative according to claim 1, wherein the silane compound represented by the formula (1) is reacted in the presence of an alkali metal or an alkaline earth metal in an inert solvent.