JPH05230218A - Production of reticular polymer having skeleton comprising si-si bonds - Google Patents

Abstract

PURPOSE:To produce the title polymer safely by subjecting a specified dihalosilane to an electrode reaction under specified conditions to form a polysilane, adding a trihalosilane and/or a tetrahalosilane to this reaction system, and subjecting the entire system to an electrode reaction. CONSTITUTION:A dihalosilane of formula I (wherein R is H, alkyl, aryl, alkoxyl or amino; and X is halogen) is subjected to an electrode reaction under conditions in which a perchlorate is used as a supporting electrolyte, an aprotic solvent is used as the solvent, Mg, Cu or Al is used as an anode, and a conductive material of the same or different kind is used as a cathode to form a linear polysilane of formula II (wherein n is 10-100), and a trihalosilane of formula III and/or a tetrahalosilane of formula IV are added as such to this reaction system. The entire system is subjected to an electrode reaction under conditions in which the polarity of the electrodes is changed at a definite time interval of 1-20sec to obtain the title polymer comprising structural units of formula V and structural units of formulas VI and/or VII.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a linear polysilane by an electrode reaction, and then using this as a raw material, a subsequent electrolytic reaction to produce a network polymer having a Si-Si bond as a skeleton.

[0002]

2. Description of the Related Art A network polymer having a Si-Si bond as a skeleton has been attracting attention as a useful material such as a ceramic precursor and an optical / electronic material. In other words, this polymer has the same excellent heat resistance stability as the silicon network polymer, and also has the properties of both materials that it has the same performance as polysilane in terms of optical and electronic functions. have.

Linear polysilane exhibits ultraviolet absorption around 300 nm and is expected as an optoelectronic functional material. However, since this material usually decomposes when heated to 500 ° C or higher, it has a problem in heat resistance {Polymer
Preprints, Japan Vol.40, No.10, 3781-3783 (1991)}.
In order to solve such a problem, a linear polysilane having a molecular weight in a certain range and having halogen atoms at both ends is first synthesized, and this is crosslinked with trihalosilane or tetrahalosilane to form a network polymer. A method of synthesizing can be considered. However, this method has not been implemented so far. This is a method conventionally used in synthesizing linear polysilanes, that is, dichlorosilanes are used as a starting material and 1% together with sodium metal.
In the method of heating at a temperature of 00 ° C. or higher and stirring, it is practically impossible to control the molecular weight, so that it is not possible to obtain a linear polysilane having a desired molecular weight. Even if a linear polysilane having a desired molecular weight is obtained, this method uses a large amount of alkali metal and thus has a serious problem in safety, and is suitable for industrial large-scale production. Absent.

As a method for synthesizing linear polysilane,
A method using a non-hazardous electrode reaction capable of controlling the molecular weight has been reported {J.Chem.Soc.Commun., 1990,116.
0; Electrochem. Acta, 35, 1867 (1990); Electrochemistry and Industrial Physical Chemistry Vol. 59, No. 5, 421 (1991);
No. 04893}. According to these methods, the molecular weight can be controlled by controlling the amount of electricity applied, and thus linear polysilane having a molecular weight within a certain range can be easily produced.
However, since the production of the network polymer is not considered in these methods, it is not possible to know how to obtain the network polymer.

[0005]

SUMMARY OF THE INVENTION Therefore, the present invention is based on S
It is a main object to provide a method capable of safely producing a network polymer having an i-Si bond as a skeleton on an industrial scale.

[0006]

Means for Solving the Problems As a result of intensive studies in view of the state of the art as described above, the present inventor has electrolyzed a linear polysilane having halogen atoms at both ends and having a molecular weight in a certain range. After manufacturing by reaction, at least one of trihalosilane and tetrahalosilane is added in the same reaction system.
It has been found that when the seed is added and the electrode reaction is subsequently carried out, the problems of the prior art are substantially eliminated or greatly reduced.

In the case of irradiating the reactor or the reaction solution with ultrasonic waves in the electrode reaction as described above, the reaction time is shortened and the molecular weight of the reaction product is increased.
It was also found that its yield was increased.

That is, the present invention provides the following method for producing a network polymer having a Si-Si bond as a skeleton: A method for producing a network polymer having a Si-Si bond as a skeleton, which comprises (a) a general formula:

[0009]

[Chemical 29]

(In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group, and two Rs may be the same or different; X is
Dihalosilane represented by a halogen atom) is used as a supporting electrolyte, a perchlorate is used, an aprotic solvent is used as a solvent, and Mg, Cu or Al is used as an anode,
By subjecting the same or different conductive material as these to the electrode reaction using as a cathode, the general formula

[0011]

[Chemical 30]

(In the formula, R and X are as defined above; n
Is 10 to 100. ) Forming a linear polysilane having halogens at both ends, and (b) a general formula in a reaction system containing the linear polysilane represented by the general formula (2).

[0013]

[Chemical 31]

(In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X
Represents a halogen atom. ) Trihalosilane and / or general formula

[0015]

[Chemical 32]

(In the formula, X represents a halogen element.)
The tetrahalosilane represented by

[0017]

[Chemical 33]

(Wherein R is as defined above) and the general formula

[0019]

[Chemical 34]

(Wherein R is as defined above) and / or the general formula

[0021]

[Chemical 35]

Si--Si consisting of a structural unit represented by
A method for producing a network polymer having a bond as a skeleton.

2. The method according to item 1 above, wherein the step (b) is performed under irradiation of ultrasonic waves.

3. A method for producing a network polymer having a Si-Si bond as a skeleton, which comprises (a) a general formula:

[0025]

[Chemical 36]

(In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group, and two Rs may be the same or different; X is
A dihalosilane represented by a halogen atom) is used as a supporting electrolyte under irradiation with ultrasonic waves, a perchlorate is used as a solvent, an aprotic solvent is used as a solvent, and Mg, Cu or Al is used as an anode. By subjecting an electrode reaction using different kinds of conductive materials as a cathode,

[0027]

[Chemical 37]

(In the formula, R and X are as defined above; n
Is 10 to 100. ) To form a linear polysilane having halogens at both ends, and (b) a reaction system containing the linear polysilane represented by the general formula (2).

[0029]

[Chemical 38]

(In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X
Represents a halogen atom. ) Trihalosilane and / or general formula

[0031]

[Chemical Formula 39]

(In the formula, X represents a halogen element.)
The tetrahalosilane represented by

[0033]

[Chemical 40]

(Wherein R is the same as above) and the general formula

[0035]

[Chemical 41]

(Wherein R is as defined above) and / or the general formula

[0037]

[Chemical 42]

Si--Si consisting of the structural unit represented by
A method for producing a network polymer having a bond as a skeleton.

4. Item 4. The method according to Item 3, wherein the step (b) is performed under irradiation of ultrasonic waves.

5. A method for producing a network polymer having a Si-Si bond as a skeleton, which comprises (a) a general formula:

[0041]

[Chemical 43]

(In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group, and two Rs may be the same or different; X is
A dihalosilane represented by a halogen atom) is used as a supporting electrolyte, a perchlorate is used as a solvent, an aprotic solvent is used as a solvent, and Mg, Cu or Al is used as one electrode, and the same or different conductivity as those of these is used. By using the material as the other electrode and subjecting it to an electrode reaction in which the polarity of the electrode is switched at fixed time intervals of 10 seconds or more and 3 minutes or less, the general formula

[0043]

[Chemical 44]

(In the formula, R and X are the same as above; n
Is 10 to 100. ) Forming a linear polysilane having halogens at both ends, and (b) a general formula in a reaction system containing the linear polysilane represented by the general formula (2).

[0045]

[Chemical 45]

(In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X
Represents a halogen atom. ) Trihalosilane and / or general formula

[0047]

[Chemical 46]

(In the formula, X represents a halogen element.)
The tetrahalosilane represented by

[0049]

[Chemical 47]

(Wherein R is the same as above) and the general formula

[0051]

[Chemical 48]

(Wherein R is as defined above) and / or the general formula

[0053]

[Chemical 49]

Si--Si consisting of a structural unit represented by
A method for producing a network polymer having a bond as a skeleton.

6. Item 6. The method according to Item 5, wherein the step (b) is performed under irradiation of ultrasonic waves.

7. A method for producing a network polymer having a Si-Si bond as a skeleton, which comprises (a) a general formula:

[0057]

[Chemical 50]

(In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group, and two Rs may be the same or different; X is
A dihalosilane represented by a halogen atom) is used as a supporting electrolyte under the irradiation of ultrasonic waves, aprotic solvent is used as a solvent, and Mg, Cu or Al is used as one electrode, and By using the same or different conductive material as the other electrode and subjecting it to an electrode reaction in which the polarity of the electrode is switched at fixed time intervals of 10 seconds or more and 3 minutes or less, the general formula

[0059]

[Chemical 51]

(In the formula, R and X are the same as above; n
Is 10 to 100. ) Forming a linear polysilane having halogens at both ends, and (b) a general formula in a reaction system containing the linear polysilane represented by the general formula (2).

[0061]

[Chemical 52]

(In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X
Represents a halogen atom. ) Trihalosilane and / or general formula

[0063]

[Chemical 53]

(In the formula, X represents a halogen element.)
The tetrahalosilane represented by the formula (1) is added as it is and subjected to an electrode reaction in which the polarity of the electrode is switched at a constant time interval of 1 second or more and 20 seconds or less.

[0065]

[Chemical 54]

(Wherein R is the same as above) and the general formula

[0067]

[Chemical 55]

(Wherein R is as defined above) and / or the general formula

[0069]

[Chemical 56]

Si--Si consisting of a structural unit represented by
A method for producing a network polymer having a bond as a skeleton.

8. Item 8. The method according to Item 7, wherein the step (b) is performed under irradiation of ultrasonic waves.

In the following, the above items 1, 2, 3 and 4,
5-6 and 7-8 are the first invention of the present application,
They are called the second invention of the present application, the third invention of the present application, and the fourth invention of the present application, and when they are summarized, they are simply referred to as the present invention.

In the step (a) of the first invention of the present application, the compound used as a starting material is a compound represented by the general formula:

[0074]

[Chemical 57]

A dihalosilane represented by the formula (wherein R and X are the same as described above).

In the dihalosilane represented by the general formula (1), examples of the alkyl group include those having 1 to 10 carbon atoms, and among these, those having 1 to 6 carbon atoms are more preferable. As the aryl group, a phenyl group and a carbon number of 1
Substituted phenyl groups, p-alkoxyphenyl groups, naphthyl groups and the like having at least one kind of the alkyl groups of to 6 as a substituent are exemplified. Examples of the alkoxy group include those having 1 to 10 carbon atoms, and among these, those having 1 to 6 carbon atoms are more preferable. When R is the above amino group or organic substituent, at least one of the hydrogen atoms may be further substituted with another functional group such as an alkyl group, an aryl group or an alkoxy group.

In the general formula (1), X represents a halogen atom (Cl, F, Br, I). Cl is more preferable as the halogen atom.

In the step (a) of the first invention of the present application, one type of the compound represented by the general formula (1) may be used, or two or more types may be used in combination. These compounds are
It is preferable that the purity is as high as possible. For example, it is preferable to use by distilling before use.

The reaction product obtained in the step (a) of the first invention of the present application has the general formula

[0080]

[Chemical 58]

(In the formula, R, X and n are the same as described above, and two Rs may be the same or different.) A linear polysilane having halogen atoms at both ends.

In the reaction in the step (a) of the first invention of the present application, the compound represented by the general formula (1) is used by dissolving it in a solvent.

As the solvent, aprotic solvents can be widely used, and more specifically, tetrahydrofuran, 1,
2-dimethoxyethane, bis (2-methoxyethyl) ether, p-dioxane, propylene carbonate, acetonitrile, dimethylformamide, dimethylsulfoxide, methylene chloride and the like are exemplified. These solvents can be used alone or as a mixture of two or more kinds. As the solvent, it is more preferable to use an ether solvent such as tetrahydrofuran, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether or p-dioxane, alone or in a mixture with another solvent.
Particularly preferred solvents are tetrahydrofuran and 1,2
-Dimethoxyethane. If the concentration of the compound (1) in the solvent is too low, the current efficiency will decrease, whereas if it is too high, the supporting electrolyte may not dissolve. Therefore, the concentration of the raw materials in the solvent is usually 0.0
It is about 5 to 20 mol / l, more preferably 0.1 to 1
5 mol / l or so, particularly preferably 0.2 to 13 mol / l
It is about l.

Examples of the supporting electrolyte used in the present invention include alkali metal perchlorates such as sodium perchlorate and lithium perchlorate; and tetraalkylammonium perchlorate such as tetra-n-butylammonium perchlorate. Use chlorate. These supporting electrolytes may be used alone or in combination of two or more kinds. Among these supporting electrolytes, lithium perchlorate and tetra-n-butylammonium perchlorate are more preferable, and lithium perchlorate is most preferable. If the concentration of the supporting electrolyte is too low, the reaction does not proceed sufficiently because the ionic conductivity given to the reaction solution is low, whereas if it is too high, an excessive current flows and the reaction is necessary for the reaction. The electric potential cannot be obtained. Therefore, the concentration of the supporting electrolyte in the solvent is usually about 0.05 to 5 mol / l, more preferably about 0.1 to 3 mol / l, and particularly preferably about 0.15 to 1.2 mol / l. Is.

In the first invention of the present application, as the anode, M
One of g, Cu and Al or an alloy containing these metals as a main component is used, and a conductive material (Ni, Co, Pt, etc.) which is the same as or different from these is used as the cathode. As a material for both electrodes, Mg, Al or an alloy containing these metals as main components is more preferable, and Mg is most preferable. The shape of the electrode is not particularly limited as long as the current can be stably supplied, but a rod shape, a plate shape, a cylinder shape, a coiled shape of a plate shape body, or the like is preferable. It is preferable to remove the oxide film as much as possible from the surface of the electrode. The oxide film can be removed from the electrode by any method. For example, the electrode is washed with acid, then washed with ethanol and ether, and dried under reduced pressure. The electrode is polished under a nitrogen atmosphere. It can be carried out by a method or a combination of these methods.

When carrying out the step (a) of the first invention of the present application, the compound represented by the general formula (1) and the supporting electrolyte are housed together with a solvent in a sealable reaction vessel equipped with an anode and a cathode, and preferably, The electrode reaction is performed by supplying a predetermined amount of current while mechanically or magnetically stirring. The reaction vessel may have a dry atmosphere, but a dry nitrogen or inert gas atmosphere is more preferable, and a deoxygenated and dry nitrogen or inert gas atmosphere is most preferable. The amount of electricity applied is usually 1 F / mol or more based on the halogen atom in the raw material, and the molecular weight can be controlled by adjusting the amount of electricity applied. The temperature during the reaction may be within the temperature range of the boiling point of the solvent used or less. The reaction time may be appropriately determined according to the resistance of the electrolytic solution related to the amount of the supporting electrolyte, the desired molecular weight of the linear polysilane, and the like. In the step (a) of the first invention of the present application, there is no need to use a diaphragm which is indispensable in a normal electrode reduction reaction, and the operation is simple and advantageous.

In the step (b) of the first invention of the present application, a general formula is added to the reaction system containing the linear polysilane represented by the general formula (2) obtained as described above.

[0088]

[Chemical 59]

(Wherein R and X are the same as defined above) and the general formula

[0090]

[Chemical 60]

At least one tetrahalosilane represented by the formula (wherein X is the same as above) is directly added to the electrode reaction in which the polarity of the electrode is switched at a constant time interval of 1 second to 20 seconds. General formula

[0092]

[Chemical formula 61]

(Wherein R is as defined above) and a general formula

[0094]

[Chemical formula 62]

Structural unit represented by and general formula

[0096]

[Chemical 63]

A network polymer containing at least one structural unit represented by and having Si-Si units as a skeleton is produced.

The mixing ratio of the compounds (2), (3) and (4) in the step (b) of the first invention of the present application is the same as the compound (2):
Compound (3): Compound (4) = 1: 100 to 10,000
It is preferable to set it as the range. In the case of this mixing ratio, the mixture is soluble in an organic solvent, and the resulting polymer exhibits a composite function having both properties of a linear polysilane and a network polymer, which is preferable. is there.

The reaction conditions in the step (b) of the first invention of the present application are substantially the same as those in the step (a) except that the polarity of the electrode is switched at a time interval of 1 to 20 seconds. The polarities are switched at regular time intervals of about 1 second to 20 seconds in order to realize a strong reducing system. In the step (b) of the first invention of the present application, when both electrodes are made of the same material, metal ions (for example, Mg ²⁺ ) are melted out between both electrodes and the migration is performed,
This is preferable because the consumption of the electrodes is reduced and the energization time can be extended.

In step (b) of the first invention of the present application, ultrasonic waves may be applied to the reactor or the reaction solution during the electrode reaction. The method of irradiating ultrasonic waves during the electrode reaction is not particularly limited, but a method of irradiating by accommodating the reactor in an ultrasonic bath, a method of irradiating by irradiating an ultrasonic oscillator in the reactor Are exemplified. The frequency of ultrasonic waves is 10
It is preferably about 70 kHz. The output of ultrasonic waves may be appropriately determined according to the reaction conditions such as the type of raw material, the amount of reaction solution, the shape and size of the reaction vessel and electrode, the material and surface area of the electrode, etc. It is in the range of about 0.01 to 24 kW. By such ultrasonic irradiation, the reaction time is drastically shortened to about 1/3 to 2/3 of that in the case where ultrasonic waves are not irradiated, the molecular weight is increased, and the yield is remarkably improved. In the present invention, the ultrasonic wave is satisfactorily stirred, but if necessary, a mechanical means may be used together.

The network polymer obtained in the step (b) of the first invention of the present application varies depending on the kind of raw materials, reaction conditions, etc.
Usually, the average molecular weight is about 2000 to 1,000,000.

The step (a) of the second invention of the present application is carried out under the general formula under irradiation of ultrasonic waves.

[0103]

[Chemical 64]

The dihalosilane represented by the formula (wherein R and X are the same as above) is subjected to an electrode reaction.

The step (a) of the second invention of the present application is the same as the step (a) of the first invention of the present application except that the irradiation of ultrasonic waves is performed. Also, the irradiation of ultrasonic waves is the first in the present application.
It may be carried out under the same conditions as in the step (b) of the invention. By this ultrasonic irradiation, the reaction time required for producing linear polysilane is significantly shortened, and the yield thereof is also significantly improved.

In the step (b) of the second invention of the present application, the linear polysilane represented by the general formula (2) obtained in the step (a) is generally used in the same manner as the step (b) of the first invention of the present application. The trihalosilane represented by the formula (3) and the general formula (4)
At least one tetrahalosilane represented by the formula (3) is directly added and subjected to an electrode reaction in which the polarity of the electrode is switched at a fixed time interval of 1 second or more and 20 seconds or less, and the structure represented by the general formula (5) A network polymer containing a unit and at least one kind of the structural unit represented by the general formula (6) and the structural unit represented by the general formula (7) and having a Si—Si unit as a skeleton is produced.

A mixing ratio of the compound (2), the compound (3) and the compound (5) in the step (b) of the second invention of the present application,
The reaction conditions and the like may be the same as in step (b) of the first invention of the present application. Also, in the step (b) of the first invention of the present application, it is preferable that both electrodes are made of the same material.

Also in the step (b) of the second invention of the present application, ultrasonic waves can be applied to the reactor or the reaction solution during the electrode reaction.

The network polymer obtained in the step (b) of the second invention of the present application also differs depending on the type of raw material, reaction conditions, etc.
Usually, the average molecular weight is about 2000 to 1,000,000.

The step (a) of the third invention of the present application differs from the step (a) of the first invention of the present application in that the polarity of the electrodes is switched at a constant time interval of 10 seconds or more and 3 minutes or less. Absent. If the time interval of polarity switching is too short, the reaction efficiency will decrease, while if it is too long, the reaction time will increase and the yield will decrease.

Also in the step (a) of the third invention of the present application, when both electrodes are made of the same kind of material, metal ions (for example, Mg ²⁺ ) are dissolved between both electrodes and the migration is performed. This is preferable because the consumption of the electrodes is reduced and the energization time can be extended.

Also in the step (b) of the third invention of the present application, in the same manner as the step (b) of the first invention of the present application, the linear polysilane represented by the general formula (2) obtained in the previous step (a) is obtained. At least one of the trihalosilane represented by the general formula (3) and the tetrahalosilane represented by the general formula (4) is directly added, and the polarity of the electrode is changed at regular intervals of about 1 second to 20 seconds. Subject to an electrode reaction for switching, containing a structural unit represented by the general formula (5) and at least one structural unit represented by the general formula (6) and a structural unit represented by the general formula (7), A network polymer having a Si-Si unit as a skeleton is produced.

A mixing ratio of the compound (2), the compound (3) and the compound (5) in the step (b) of the third invention of the present application,
The reaction conditions and the like may be the same as in step (b) of the first invention of the present application. Also, in the step (b) of the third invention of the present application, it is preferable that both electrodes are made of the same material.

Also in the step (b) of the third invention of the present application, ultrasonic waves can be applied to the reactor or the reaction solution during the electrode reaction.

The network polymer obtained in the step (b) of the third invention of the present application also differs depending on the type of raw material, reaction conditions, etc.
Usually, the average molecular weight is about 2000 to 1,000,000.

The step (a) of the fourth invention of the present application is the same as the step (a) of the third invention of the present application except that the irradiation of ultrasonic waves is performed. The ultrasonic wave irradiation may be performed in the same manner as in the step (b) of the first invention of the present application.

Also in the step (b) of the fourth invention of the present application, the linear polysilane represented by the general formula (2) obtained in the previous step (a) is obtained in the same manner as the step (b) of the first invention of the present application. At least one of the trihalosilane represented by the general formula (3) and the tetrahalosilane represented by the general formula (4) is directly added, and the polarity of the electrode is changed at regular intervals of about 1 second to 20 seconds. Subject to an electrode reaction for switching, containing a structural unit represented by the general formula (5) and at least one structural unit represented by the general formula (6) and a structural unit represented by the general formula (7), A network polymer having a Si-Si unit as a skeleton is produced.

A mixing ratio of the compound (2), the compound (3) and the compound (5) in the step (b) of the fourth invention of the present application,
The reaction conditions and the like may be the same as in step (b) of the first invention of the present application.

Also in the step (b) of the fourth invention of the present application, ultrasonic waves can be applied to the reactor or the reaction solution during the electrode reaction.

The network polymer obtained in the step (b) of the fourth invention of the present application also differs depending on the type of raw material, reaction conditions, etc.
Usually, the average molecular weight is about 2000 to 1,000,000.

In the present invention, it is desirable to remove water in the solvent and the supporting electrolyte in advance in order to suppress the introduction of oxygen into the skeleton of the produced polymer. For example, when tetrahydrofuran or 1,2-dimethoxyethane is used as the solvent, it is preferable to previously dry it with sodium-benzophenone ketyl. Further, in the case of a supporting electrolyte, it is preferable to dry by heating under reduced pressure or to remove water by adding a substance that easily reacts with water and can be easily removed (for example, trimethylchlorosilane).

[0122]

According to the present invention, the following remarkable effects are achieved.

(A) Since no alkali metal is used, Si-Si can be safely and easily used in industrial scale production.
A network polymer having a bond as a skeleton can be produced.

(B) By adjusting the energization amount and the like,
The molecular weight of the network polymer having a Si-Si bond as a skeleton can be controlled.

(C) Since a stable and safe substance is used as the electrode, a network polymer having a Si--Si bond as a skeleton can be produced without risk of environmental pollution.

(D) The formation of Si-O-Si bonds in the skeleton can be significantly suppressed. (E) Since it is not necessary to use a diaphragm, the diaphragm is not clogged and the operation is simple.

(F) When ultrasonic waves are applied during the electrode reaction, the reaction time is greatly shortened to about 2/3 to 1/3, the molecular weight of the reaction product is increased, and the yield is also increased. Significantly improved.

[0128]

EXAMPLES Examples will be shown below to further clarify the features of the present invention.

Example 1 (a) Step Three-way cock and Mg electrode (1 cm × 1 cm × 5 cm; its surface was washed with dilute sulfuric acid, then with ethanol and ether, dried under reduced pressure, and polished under a nitrogen atmosphere. , With the oxide film on the surface removed)
A 1-necked flask (hereinafter referred to as a reactor) was charged with 1 g of anhydrous lithium perchlorate, and heated and depressurized to 1 mmHg at 50 ° C. (6
Hours), after drying the lithium perchlorate, deoxygenated dry nitrogen was introduced into the reactor, and tetrahydrofuran 15 was previously dried with sodium-benzophenone ketyl.
ml was added. To this was added 1.45 ml of methylphenyldichlorosilane that had been distilled in advance, and the reactor was kept at room temperature with a water bath while being energized by a constant voltage power source. At this time, using a commutator, the polarities of the two electrodes were changed every 15 seconds, and electricity was applied for 55 hours so that the amount of electricity applied was 2 F / mol based on chlorine in the monomer.

A part of the product was collected and subjected to analysis. It was confirmed that a linear polysilane having a weight average molecular weight of 3340 was formed.

As a result of elemental analysis, the oxygen content in this linear polysilane was 0.1% or less, and Si--O--Si
It was confirmed that the content rate of was extremely low.

Step (b) Next, 0.16 ml of phenyltrichlorosilane was introduced into the above reactor, the polarities of the two electrodes were changed every 15 seconds, and 2 F / mol
The electricity was applied for 7 hours so that the amount of electricity would be.

As a result, Si having a weight average molecular weight of 9650 was obtained.
A network polymer having a —Si bond as a skeleton was formed with a yield of 42%.

Example 2 In the step (a), the reactor was operated with an output of 60 W and a frequency of 45.
The electrode reaction was performed in the same manner as in Example 1 except that the substrate was immersed in a KHz ultrasonic cleaner and irradiated with ultrasonic waves. As a result, a network polymer having a weight average molecular weight of 12700 and having a Si—Si bond as a skeleton was obtained at a yield of 69%.

Example 3 An electrode reaction was carried out in the same manner as in Example 2 except that one electrode was made of Mg, the other electrode was made of Ni, and the polarity of the electrodes was not switched. A network polymer having a molecular weight of 10500 and having a Si-Si bond as a skeleton was obtained at a yield of 53%.

Example 4 An electrode reaction was carried out in the same manner as in Example 1 except that tetra-n-butylammonium perchlorate was used in place of lithium perchlorate.

As a result, Si having a weight average molecular weight of 8500 was obtained.
-59% yield of network polymer having Si bond as a skeleton
Obtained in.

Example 5 An electrode reaction was carried out in the same manner as in Example 1 except that 1,2-dimethoxyethane was used as the solvent. As a result, a network polymer having a weight average molecular weight of 8700 and having a Si—Si bond as a skeleton was used. Was obtained with a yield of 62%.

Example 6 1.13 ml of methylphenyldichlorosilane was used as a raw material in the step (a), and 0.48 phenyltrichlorosilane was added as a raw material in the step (b).
The electrode reaction was carried out in the same manner as in Example 1 except that ml was used.

As a result, Si having a weight average molecular weight of 6550 was obtained.
-43% yield of reticulated polymer having Si bond as a skeleton
Obtained in.

Example 7 0.81 ml of methylphenyldichlorosilane was used as a raw material in the step (a), and phenyltrichlorosilane 0.80 was used as an additional raw material in the step (b).
The electrode reaction was carried out in the same manner as in Example 1 except that ml was used.

As a result, Si having a weight average molecular weight of 4760 was obtained.
-47% yield of reticulated polymer having Si bond as a skeleton
Obtained in.

Example 8 An electrode reaction was carried out in the same manner as in Example 7 except that 7.5 ml of tetrahydrofuran was used as the solvent.
A network polymer having a weight average molecular weight of 6370 and having a Si—Si bond as a skeleton was obtained at a yield of 23%.

Example 9 An electrode reaction was carried out in the same manner as in Example 7 except that the two electrodes were made of aluminum.
A network polymer having a —Si bond as a skeleton was obtained.

Example 10 An electrode reaction was carried out in the same manner as in Example 7 except that the two electrodes were made of copper, and a similar network polymer having a Si—Si bond as a skeleton was obtained.

Example 11 An electrode reaction was conducted in the same manner as in Example 1 except that 1.0 ml of methyl-n-hexyldichlorosilane was used as the raw material in the step (a), and the corresponding Si-Si was obtained.
A network polymer having a bond as a skeleton was obtained.

Example 12 An electrode reaction was carried out in the same manner as in Example 11 except that 0.57 ml of tetrachlorosilane was used as an addition raw material in the step (b), and a network having a corresponding Si—Si bond as a skeleton was formed. A polymer was obtained.

Example 13 An electrode reaction was carried out in the same manner as in Example 1 except that the amount of electricity applied was 1.5 F / mol based on chlorine in the raw material in the step (a).

As a result, Si having a weight average molecular weight of 3130 was obtained.
A network polymer having a —Si bond as a skeleton was obtained at a yield of 39%.

Example 14 The electrode reaction was carried out in the same manner as in Example 1 except that the amount of electricity applied based on chlorine in the raw material in step (a) was set to 1.0 F / mol.

As a result, Si having a weight average molecular weight of 2540
A network polymer having a —Si bond as a skeleton was obtained with a yield of 28%. .

Example 15 An electrode reaction was carried out in the same manner as in Example 2 except that 0.11 ml of tetrachlorosilane was used as an additional raw material in the step (b).

As a result, S having a weight average molecular weight of 14900 was obtained.
A network polymer having an i-Si bond as a skeleton was obtained in a yield of 42.
Obtained in%.

Example 16 An electrode reaction was carried out in the same manner as in Example 7 except that 0.11 ml of tetrachlorosilane was used as the additional raw material in the step (b).

As a result, Si having a weight average molecular weight of 6900 was obtained.
21% yield of a network polymer having a Si bond as a skeleton.
Obtained in.

Example 17 0.16 ml of phenyltrichlorosilane and 0.01 ml of tetrachlorosilane were added as starting materials in step (b).
The electrode reaction was performed in the same manner as in Example 2 except that was used.

As a result, S having a weight average molecular weight of 15900 was obtained.
The yield of the reticulated polymer having an i-Si bond as a skeleton was 64.
Obtained in%.

Reference Example 1 The results of thermogravimetric analysis of the network polymer having a Si—Si bond as the skeleton obtained in Example 1 are shown in FIG.

FIG. 2 shows the result of thermogravimetric analysis of a conventional linear polysilane having a Si—Si bond as the main chain.

From the comparison between FIG. 1 and FIG.
The excellent heat resistance of the network polymer having an i-Si bond as a skeleton is clear.

Reference Example 2 FIG. 3 shows an absorption spectrum of a known silicon network polymer.

FIG. 4 shows an absorption spectrum of a conventional linear polysilane having a Si—Si bond as a main chain.

FIG. 5 shows an absorption spectrum diagram of the network polymer having the Si—Si bond as a skeleton obtained in Example 1.

From the comparison of FIGS. 3 to 5, Si according to the present invention
It is clear that the network polymer having the —Si bond as the skeleton has the optical properties of both the polysilane and the silicon network polymer.

[Brief description of drawings]

FIG. 1 is a graph showing a thermal analysis result of a network polymer having a Si—Si bond as a skeleton obtained in Example 1.

FIG. 2 is a graph showing a thermal analysis result of a conventional linear polymer having a Si—Si bond as a main chain.

FIG. 3 is a graph showing an absorption spectrum of a known silicon network polymer.

FIG. 4 is a graph showing an absorption spectrum of a conventional linear polymer having a Si—Si bond as a main chain.

FIG. 5 is a graph showing an absorption spectrum of a network polymer having a Si—Si bond as a skeleton obtained in Example 1.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ryoichi Nishida 4-1-2, Hirano-cho, Chuo-ku, Osaka-shi, Osaka Within Osaka Gas Co., Ltd. (72) Shin-ichi Kawasaki 4-chome, Hirano-cho, Chuo-ku, Osaka-shi, Osaka No. 1 and 2 in Osaka Gas Co., Ltd.

Claims (8)

[Claims] 1. A method for producing a network polymer having a Si—Si bond as a skeleton, which comprises (a) a general formula: (In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or an amino group, and two Rs may be the same or different. X represents a halogen atom). A perchlorate salt is used as a supporting electrolyte, dihalosilane is used, an aprotic solvent is used as a solvent, and Mg, Cu or Al is used as an anode, and a conductive material of the same or different type is used as a cathode for an electrode reaction. Therefore, the general formula: (In the formula, R and X are the same as above .; n is 10 to 10).
It is 0. (B) forming a linear polysilane having halogens at both ends, and (b) a reaction system containing the linear polysilane represented by the general formula (2). (In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X represents a halogen atom.) And / or a trihalosilane represented by the general formula: (In the formula, X represents a halogen element.) Tetrahalosilane represented by the formula is added as it is, and subjected to an electrode reaction in which the polarity of the electrode is switched at a constant time interval of 1 second or more and 20 seconds or less. Chemical 5] (Wherein R is the same as above) and a general formula: (Wherein R is the same as above) and / or the general formula: A method for producing a reticulated polymer having a Si-Si bond as a skeleton, which comprises a structural unit represented by: 2. The method according to claim 1, wherein the step (b) is performed under irradiation of ultrasonic waves. 3. A method for producing a network polymer having a Si—Si bond as a skeleton, which comprises (a) a general formula: (In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or an amino group, and two Rs may be the same or different. X represents a halogen atom). Dihalosilane is used as a supporting electrolyte under ultrasonic irradiation, an aprotic solvent is used as a solvent, Mg, Cu or Al is used as an anode, and a conductive material of the same kind or different kind is used as a cathode. By subjecting it to an electrode reaction to be used, a compound of the general formula: (In the formula, R and X are the same as above .; n is 10 to 10).
It is 0. (B) forming a linear polysilane having halogens at both ends, and (b) a reaction system containing the linear polysilane represented by the general formula (2). (In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X represents a halogen atom.) And / or a trihalosilane represented by the general formula: (In the formula, X represents a halogen element.) Tetrahalosilane represented by the formula is added as it is, and subjected to an electrode reaction in which the polarity of the electrode is switched at a constant time interval of 1 second or more and 20 seconds or less. Chemical 12] (Wherein R is the same as above) and a general formula: (Wherein R is the same as above) and / or the general formula: A method for producing a reticulated polymer having a Si-Si bond as a skeleton, which comprises a structural unit represented by: 4. The method according to claim 3, wherein the step (b) is performed under irradiation of ultrasonic waves. 5. A method for producing a network polymer having a Si—Si bond as a skeleton, which comprises (a) a general formula: (In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or an amino group, and two Rs may be the same or different. X represents a halogen atom). Dihalosilane is used as the supporting electrolyte, perchlorate is used as the solvent, aprotic solvent is used as the solvent, Mg, Cu or Al is used as one pole, and the same or different conductive material as these is used as the other pole. ,
By subjecting it to an electrode reaction in which the polarity of the electrode is switched at a constant time interval of 10 seconds or more and 3 minutes or less, the general formula: (In the formula, R and X are the same as above .; n is 10 to 10).
It is 0. ), A step of forming a linear polysilane having halogens at both ends, and (b) a reaction system containing the linear polysilane represented by the general formula (2). (In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X represents a halogen atom.) And / or a trihalosilane represented by the general formula: (In the formula, X represents a halogen element.) Tetrahalosilane represented by the formula is added as it is, and subjected to an electrode reaction in which the polarity of the electrode is switched at a constant time interval of 1 second or more and 20 seconds or less. Chemical 19] (Wherein R is as defined above) and a general formula: (Wherein R is the same as above) and / or the general formula: A method for producing a reticulated polymer having a Si-Si bond as a skeleton, which comprises a structural unit represented by: 6. The method according to claim 5, wherein the step (b) is performed under irradiation of ultrasonic waves. 7. A method for producing a network polymer having a Si—Si bond as a skeleton, which comprises (a) a general formula: (In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or an amino group, and two Rs may be the same or different. X represents a halogen atom). A perchlorate is used as a supporting electrolyte under the irradiation of ultrasonic waves with dihalosilane, an aprotic solvent is used as a solvent, and Mg, Cu or Al is used as one electrode, and a conductive material of the same kind or different kind from these is used. By using it as the other electrode and subjecting it to an electrode reaction in which the polarity of the electrode is switched at a constant time interval of 10 seconds or more and 3 minutes or less, the general formula: (In the formula, R and X are the same as above .; n is 10 to 10).
It is 0. ), A step of forming a linear polysilane having halogens at both ends, and (b) a reaction system containing the linear polysilane represented by the general formula (2). (Wherein R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X represents a halogen atom) and / or a general formula: (In the formula, X represents a halogen element.) Tetrahalosilane represented by the formula is added as it is, and subjected to an electrode reaction in which the polarity of the electrode is switched at a constant time interval of 1 second or more and 20 seconds or less. Chemical 26] (Wherein R is the same as above) and a general formula: (Wherein R is as defined above) and / or the general formula A method for producing a reticulated polymer having a Si-Si bond as a skeleton, which comprises a structural unit represented by: 8. The method according to claim 7, wherein the step (b) is performed under irradiation of ultrasonic waves.