JPH036231A - New polymer and its use - Google Patents

Abstract

PURPOSE:To obtain a new functional polymer contg. silicon-silicon bonds and 1,5-naphthylene groups as alternating repeating units and suitably used as an electrically conductive material. CONSTITUTION:A new polymer, a polysilane compd. of formula I (wherein R<1> and R<2> are each independently alkyl, aryl, or aralkyl; and (n)>=2), can be produced, e.g. by reacting a 1,5-bis(chlorosilyl)naphthalene deriv. of formula II (wherein R<1> and R<2> are the same as in formula I) with an alkali metal in such an amt. that the alkali metal can react with chlorine atoms in said deriv., and can be used, pref. with a dopant (pref. SbF5) added, as an electrically conductive material because it has an electrical conductivity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel and useful polymer having a silicon-silicon bond in its main chain and its uses. For more details 1
The present invention provides novel and useful polymers containing alternating silicon-silicon bonds and 1°5-naphthylene groups as flip units,
and a conductive material made of this polymer.

[Conventional technology]

A polymer having a Si--Si bond in the main chain of the polymer.

It is an extremely useful material as a photosensitive material and an insulating material.

This type of polymer is described in the Journal of Polymers.
Science, Polymer Letter Edition (J,
Polymer Sci, Polymer La
tt.

Ed, ) 22.669-671 (1984), the following formula (
Polymers consisting of structural units represented by It has problems and is not put into practical use.

Furthermore, Japanese Patent Application Laid-open No. 60-61744 discloses a polymer material consisting of repeating structural units represented by the following formula Cm as a light- and radiation-sensitive organic polymer material. Limited to the case R,=Q,
Improvement is desired especially when used as a conductive material.

On the other hand, metals have traditionally been used exclusively for applications requiring electrical conductivity, and organic polymer compounds have generally been treated as insulating materials. However, among organic polymer compounds that were conventionally recognized as insulating materials, it has been discovered that polymer compounds containing silicon atoms have electrical conductivity, and such silicon-containing polymer compounds have been used as conductive materials. Attempts have been made to use it.

For example, in 1981, it was discovered that methylphenylpolysilane, a type of polysilane, was irradiated with light to form a crosslinked structure, and by adding a dopant (doping agent), this compound exhibited high electrical conductivity. has been done. However, the dopant used here is a compound such as AsF. And by using such a dopant, the above silicon-containing compound can be
It is disclosed that the conductivity is on the order of cm (JAC
S, 103.7352-7354).

However, when such a silicon-containing compound is used as a conductive material, highly toxic AsF must be used as a dopant.

Furthermore, when producing the silicon-containing compounds as described above, there are also problems in that it is difficult to control light irradiation and it is difficult to produce compounds with good properties with good reproducibility.

Further, JP-A-62-59632 discloses a matrix-like polyalkylsilane that exhibits excellent conductivity without using AsF. This publication discloses a polysilane imparted with electrical conductivity by incorporating sulfate ions into the polyalkylsilane as a dopant. The conductivity of polyalkylsilane at this time is 10''''
~10 S/am.

However, even in the conductive material made of polysilane as described above, there is still room for improvement in characteristics such as conductivity and manufacturing conditions.

[Problem of invention]

An object of the present invention is to provide a novel polymer having silicon-silicon bonds and naphthylene bonds in repeating units and useful as a functional polymer material.

Another object of the present invention is to provide a conductive material made of the above polysilane compound.

[Structure of the invention]

The present invention is the following novel copolymer and its uses.

(1) A novel polymer characterized by comprising a polysilanated metal compound represented by the following formula (13).

(2) An electrically conductive material comprising a polymer represented by the following formula [I].

1 (In the formula, R1 and R2 each independently represent a group selected from the group consisting of an alkyl group, an aryl group, and an aralkyl group, and n represents an integer of 2 or more.) The polymer of the present invention has the above-mentioned - It is a polysilane compound represented by formula [I] and has excellent electrical conductivity.

General formula [! ], the alkyl group represented by nl and nl is usually an alkyl group having 1 to 10 carbon atoms.

Preferably there are 1 to 6 alkyl groups. Examples of such alkyl groups include linear alkyl groups such as methyl group, ethyl group, n-propyl group, lobutyl group, n-hexyl group; igo-propyl group, 5aG-butyl group, 5
Secondary alkyl groups such as ee-amyl group; and tar
Examples include tertiary alkyl groups such as t-butyl group and tart-amyl group.

An aryl group is a monovalent group having at least one aromatic ring, and this aromatic ring may have a substituent.

Specific examples of such aryl groups include phenyl, naphthyl, tolyl, and xylyl groups. Among these aryl groups, phenyl groups are preferred when the polysilane compound of the present invention is used as a conductive material.

Further, an aralkyl group is a monovalent group consisting of an aliphatic hydrocarbon having at least one aromatic ring, and the aromatic ring included here may have a substituent. Specific examples include benzyl group, phenethyl group, α-methylbenzyl group, and tolyl group.

Among the above R1 and R2, the groups present simultaneously can be selected by considering the solubility of the polymer in organic solvents, and among them, R1 and R3 are methyl and ethyl, methyl and rhohexyl, respectively. , methyl and phenyl are preferred.

In the above formula (r), n is an integer of 2 or more,
Preferably it is an integer of 10 or more.

Typical polymers comprising the polysilane compound represented by the general formula [I] of the present invention include the following.

Poly[(tetramethyldisilanylene)-t,S-naphthylene], poly((1,2-dimethyl-1,2-diphenyldisilanylene)-1,5-naphthylene), poly[(tetrabuenyldisilanylene)-t,S-naphthylene], silanylene)-t, S-naphthylene],
Poly[(1,2=diethyl-1,2-dimethyldisilanylene)-1,5-naphthylene], Poly[(1,2-dimethyl-1,2-dihexyldisilanylene)-1,5-naphthylene ].

The physical properties of the polymer of the present invention as described above are as shown in the Examples below.

The polysilane compound of the present invention as described above contains, for example, a 1,5-bis(chlorosilyl)naphthalene derivative represented by the following general formula [IV] and an amount of an alkali metal capable of reacting with a chlorine atom in the derivative. It can be produced by reaction.

The bis(chlorosilyl)naphthalene derivative represented by the above formula (IV) (wherein R' and R2 represent the same as R1 and R2 in the above formula [I]) ) was reacted with 1,5-dibromonaphthalene using magnesium to produce bis(hydrosilyl)naphthalene, which was then reacted with PdCQ in carbon tetrachloride.
, or 1,5-bis(chlorosilyl)naphthalene derivatives obtained by heating in the presence of BPO (benzoylperoxide), for example, as described above, include 1,5-bis(dimethylchlorosilyl)naphthalene, 1゜5-screw (
methylethylchlorosilyl)naphthalene, 1,5-bis(methyl n-hexylchlorosilyl)naphthalene, 1,
5-bis(methylphenylchlorosilyl)naphthalene,
1,5-bis(ethylphenylchlorosilyl)naphthalene, 1j5-bis(propylphenylchlorosilyl)naphthalene, 1,5-bis(iso-propylphenylchlorosilyl)naphthalene, 1,5-bis(diphenylchlorosilyl)naphthalene , 1,5-bis(naphthylphenylchlorosilyl)naphthalene, 1,5-bis(tolylphenylchlorosilyl)naphthalene, 1゜5-bis(
benzylphenylchlorosilyl) naphthalene, ■, 5-
Examples include bis(methylbenzylchlorosilyl)naphthalene.

When using the polysilane compound of the present invention as a conductive material, 1.5-bis(
Preference is given to using methylethylchlorosilyl)naphthalene, 1,5-bis(methylphenylchlorosilyl)naphthalene.

These compounds are usually used alone, but two or more compounds can also be used in combination, for example, for the purpose of adjusting the conductivity of the resulting polysilane compound.

In the method for producing a polysilane compound of the present invention, examples of the alkali metal to be reacted with the above-mentioned 1,5-bis(chlorosilyl)naphthalene derivative include sodium metal, lithium metal, and potassium metal. These alkali metals can be used alone or
They can also be used in combination. Particularly in the present invention, it is preferable to use metallic sodium.

An example of the reaction between the above bis(chlorosilyl)naphthalene derivative and an alkali metal is shown below.

As shown in the above formula, the alkali metal is at least bis(
It is necessary to use it in an amount that allows it to react with the chlorine atom in the bis(chlorosilyl)naphthalene derivative, and it is usually used in an amount of 2 moles or more, preferably 2 to 3 moles, per 1 mole of the bis(chlorosilyl)naphthalene derivative. be done.

Such alkali metals are generally used in the form of dispersion by being dispersed in a solvent that does not have reactivity with alkali metals. Therefore, the production method of the present invention is usually carried out in a liquid phase. The solvent used in this case is a solvent that does not have reactivity with alkali metals as described above, and is also reactive with the 1,5-bis(chlorosilyl)naphthalene derivative that is the raw material. No solvent is used.

Examples of such solvents include aromatic hydrocarbon solvents,
Examples include saturated hydrocarbon solvents, unsaturated hydrocarbon solvents, and ether solvents, with aromatic hydrocarbons such as toluene, benzene, and xylene being particularly preferred. These solvents can be used alone or in combination. Moreover, the above reaction can also be carried out without using a solvent.

The reaction temperature in the above reaction is usually -20 to 200°C
, preferably in the range of 50 to 150°C.

In addition, this reaction can be carried out under any pressure condition from reduced pressure to increased pressure, but the reaction pressure is usually reduced pressure to 60 kg/a.
1, preferably in the range of 0 to 30 kg/cd, more preferably in the range of 0 to 5 kg/cd.

The reaction time in such a reaction can be appropriately set in consideration of pressure and temperature, but is usually 5 minutes to 100 hours, preferably 1 to 10 hours.

Furthermore, such reactions are usually conducted under an inert atmosphere. This reaction is usually carried out under an argon atmosphere or a nitrogen atmosphere.

For example, the polysilane compound of the present invention represented by the general formula (11) obtained as described above has conductivity, and therefore can be used as a conductive material.

When the polysilane compound of the present invention is used as a conductive material, it is preferable to add a dopant to the polysilane compound.

The electrical conductivity (σ) of the polysilane compound of the present invention is usually 104
S-C11-1 or less, but by adding a dopant, its conductivity (σ) usually increases from o, oi to IS・c
It will be about ``ut-''.

There are no particular limitations on the dopant that can be used in the present invention, and conventionally used dopants such as I2, SO
1, AsF, etc. can also be used.

5bFs can also be used. These dopants can be used alone or in combination. Among such dopants, it is preferable to use SbF in the present invention.

There are no particular limitations on the method of using the dopant as described above, and various methods can be employed, such as a method in which a film made of a polysilane compound is formed and then the dopant is applied to this film.

By using a dopant in this manner, the polysilane compound of the present invention exhibits good electrical conductivity. Therefore, this polysilane compound can be suitably used as a conductive material.

The polysilane compound of the present invention can be used not only as a conductive material as described above, but also as a photosensitive material by utilizing the optical functionality of the 5i-Si bond.

〔Effect of the invention〕

The present invention is a new and useful polysilane compound, and has great utility value.

Since this polysilane compound has both a 5i-5L bond and a naphthalene ring in its main chain, it can be effectively used as a conductive material. In particular, by using a dopant such as SbF, it has excellent conductivity. It comes to have.

〔Example〕

Next, examples of the present invention will be described.

Example 1 (1) 7.7 g of magnesium was placed in a reaction vessel for 5-bismethylphenylsilyl)naphthalene, and after drying, 50 mQ of THF was added. To this, 33.8 g of 1,5-dibromonaphthalene and 5 g of chloromethylphenylsilane
5.8 g dissolved in 200 mQ of TI(F) was added dropwise.

After stirring overnight, the mixture was hydrolyzed and extracted with ether. After drying with magnesium sulfate, remove the solvent.

Distillation under reduced pressure was performed to obtain 27.4 g (yield: 63%) of 1.5-bis(methylphenylsilyl)naphthalene.

The boiling point of this compound is 220-235°C (O,OS~0.
080 Hg), and the melting point was 69-72°C.

The results of instrumental analysis of this compound are shown below.

111 nuclear magnetic resonance spectrum (Cg D, measured in solvent, δppm) 0.66 (6H, d, J=42Hz, Mesi),
6.59 (2H, q.

J=4.2Hz, H5i), 7.07.8(14Hy
II, ring protons), 8.33 (2H
, d, J=8.0Hz, ringprotons) Infrared absorption spectrum v 5i-) 12098cm-19Me-3L 125
3cm-' Mass spectrum m/a=368 (M") Elemental analysis C34H,, SL□ Ca1c'd C7g, 20. H6,56F
ound C78,16,H6,43 palladium chloride 59, add 6m12 of carbon tetrachloride 100m+2,
A solution of 27.4 g of 1,5-bis(methylphenylsilyl)naphthalene dissolved in 200 mg of carbon tetrachloride was added dropwise to the solution, refluxed for 3 hours, and then stirred overnight at room temperature. The reaction solution was concentrated, and the resulting crystals were recrystallized from carbon tetrachloride to obtain 22.3 g (yield: 69%) of 1,5-bis(methylphenylchlorosilyl)naphthalene. The melting point of this compound was 205°C. The results of instrumental analysis of the obtained compound are as follows.

1H nuclear magnetic resonance spectrum (measured in CCL solution, δp
pm) 0.72 (68, s, MeSi), 6.84-7.6
(14H, rn.

ring protons) 7.70 (2B, d, J=8.2Hz, ring
protons) ZR spectrum (measured by KBr method) v Me-Si 1259c+a-' mass spectrum zen/e=436 (M") elemental analysis C24H,
, Si, CQ.

Ca1c'd C [i5.89, H5,07F
ound C65,72, H5,0315-bismethylphenylchlorosilylnaphthasodium 0.58g
The mixture was vigorously stirred in 15 rmu of toluene reflux to achieve dispersion, and then cooled to room temperature.

3.0 g of 1,5-bis(chloromethylphenylsilyl)naphthalene was added dropwise as a solid, and refluxed for 8 hours.
After stirring.

It was allowed to cool to room temperature. Sodium was treated with acetic acid, ethanol, and water sequentially, and extracted with benzene.

After drying with magnesium sulfate, the solution was concentrated and added dropwise to ethanol to perform reprecipitation. The obtained solid was filtered and dried, and poly[(1,2-dimethyl-1,2-diphenyldisilanylene)-1,5-naphthylene] (R in formula [l]
1=methyl group, R2=phenyl group) 1.1g (yield 4
4%).

Regarding the polysilane compound obtained in this way,
As a result of measuring the molecular weight using GPC, the weight average molecular jt (Mw) was 25,400. Moreover, the melting point of this polysilane compound was 195 to 206°C. The results of instrumental analysis of this polysilane compound are shown below.

1H nuclear magnetic resonance spectrum (CCQ, measured in solution, δ
ppm) 0.111 (6H, brs, MaSi), 6.5-8
．． 1 (16H, II, ringprotons) 13G nuclear magnetic resonance spectrum (measured in CDC et al. solution,
δppm) -2,75,-2,11 (MeSi), 124.47.
127.63°128.58.131.43.134.
98.135.23.135.61.135.86.1
38.08 (ring carbons) infrared absorption spectrum v Me-5i 1252 cm-1 Example 2 Polydisilanylene naphthylene obtained in Example 1 (formula (
1) R1=methyl group, R1=phenyl group) 1g to 10
Dissolved in 12 m dichloroethane. Using this solution, a film with a thickness of 7,300 wafers was formed on an insulating substrate using a spin code solution.

After doping this film by supplying SbF in a gas phase, the conductivity of the film was measured. Conductivity was evaluated by applying a voltage to the membrane and measuring the flowing current and voltage using the four-probe method. As a result, the conductivity (σ) of this film was 0.58 S/cn+.

Claims (2)

[Claims] (1) A novel polymer characterized by comprising a polysilane compound represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 each independently represent a group selected from the group consisting of an alkyl group, an aryl group, and an aralkyl group, and n is 2 or more. (Represents an integer.) (2) An electrically conductive material comprising a polymer represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 each independently represent a group selected from the group consisting of an alkyl group, an aryl group, and an aralkyl group, and n is 2 or more. (Represents an integer.)