JP3291564B2 - Method for producing network polymer having Si-Si bond as skeleton - Google Patents

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 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. That is, this polymer is superior to polysilane in heat resistance stability, and has a composite function having both characteristics of polysilane and silicon network polymer in optical and electronic functions.

[0003] Conventionally, a linear polymer having a Si-Si bond in the main chain has been synthesized by stirring dichlorosilanes with sodium metal at a temperature of 100 ° C or more for a long time. When the starting material is changed to two or more of dichlorosilanes, trichlorosilanes and tetrachlorosilanes according to this method, and the reaction is carried out under the same conditions, a network having Si-Si bonds as a skeleton is used. A polymer (hereinafter simply referred to as a network polymer unless otherwise required) is not formed. That is, in order to synthesize a network polymer, it is necessary to change not only the raw materials but also the reaction conditions. Therefore, for example, a synthesis method of performing ultrasonic irradiation under strong reducing conditions in the presence of sodium metal has been proposed (Polymer Bulletin, 22,253-
259 (1989)}. However, this method uses a large amount of an alkali metal, so that when producing on an industrial scale,
There is a major problem with safety and it is not practical.

[0004] As a method for synthesizing a linear polysilane,
A method using a non-hazardous electrode reaction that can control the molecular weight has been reported. J. Chem. Soc. Commun., 1990, 116
0; Electrochem. Acta, 35, 1867 (1990); Electrochemical and Industrial Physical Chemistry, Vol. 59, No. 5, 421 (1991);
04893 and so on. However, since these methods do not consider the production of a network polymer, it is impossible to know how to obtain the network polymer.

[0005]

SUMMARY OF THE INVENTION Accordingly, the present invention provides
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]

The inventor of the present invention has conducted intensive studies in view of the state of the prior art as described above. As a result, the present inventor has used a specific metal as an anode and perchlorate as a supporting electrolyte. In addition, it has been found that when specific silanes are used for an electrode reaction in which the polarities of both electrodes are switched at fixed time intervals, 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 during the electrode reaction as described above, the reaction time is shortened and the molecular weight of the reaction product increases,
It was also found that the yield increased.

[0008] That is, the present invention provides a method for producing a network polymer having the following Si-Si bond as a skeleton: A method for producing a network polymer having a Si-Si bond as a skeleton, comprising a general formula

[0009]

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(Wherein 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) and a general formula

[0011]

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(Wherein, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X
Represents a halogen atom), a perchlorate is used as a supporting electrolyte, an aprotic solvent is used as a solvent, and Mg, Cu or Al is used as one pole, and the same kind or By using a different kind of conductive material as the other electrode for an electrode reaction in which the polarity of the electrode is switched at a time interval of 1 second or more and 20 seconds or less, the general formula

[0013]

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(Wherein 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) and a general formula

[0015]

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(Wherein R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group). A network polymer having a skeleton of a Si—Si bond composed of a structural unit represented by the formula: Method.

2. A method for producing a network polymer having a Si-Si bond as a skeleton, comprising a general formula

[0018]

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(Wherein, 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) and a general formula

[0020]

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(Wherein, X represents a halogen atom), a perchlorate is used as a supporting electrolyte, and an aprotic solvent is used as a solvent.
Mg, Cu, or Al is used as one pole, and the same or different conductive material is used as the other pole, and the other pole is used for 1 second or more.
By subjecting to an electrode reaction that switches the polarity of the electrode at time intervals of less than seconds, the general formula

[0022]

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(Wherein 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) and a general formula

[0024]

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Si—Si comprising a structural unit represented by
A method for producing a network polymer having a bond as a skeleton.

3. A method for producing a network polymer having a Si-Si bond as a skeleton, comprising a general formula

[0027]

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(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 a trihalosilane represented by the general formula

[0029]

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(Wherein X represents a halogen atom), a perchlorate is used as a supporting electrolyte, and an aprotic solvent is used as a solvent.
Mg, Cu, or Al is used as one pole, and the same or different conductive material is used as the other pole, and the other pole is used for 1 second or more.
By subjecting to an electrode reaction that switches the polarity of the electrode at time intervals of less than seconds, the general formula

[0031]

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(Wherein, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group) and a general formula

[0033]

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Si—Si comprising a structural unit represented by
A method for producing a network polymer having a bond as a skeleton.

4. A method for producing a network polymer having a Si-Si bond as a skeleton, comprising a general formula

[0036]

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(Wherein R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group, and the two Rs may be the same or different; X is
A dihalosilane represented by a halogen atom) and a general formula

[0038]

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(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 a trihalosilane represented by the general formula

[0040]

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(Wherein X represents a halogen atom), perchlorate is used as a supporting electrolyte, a non-protonic solvent is used as a solvent, and Mg, Cu or Al is used. By conducting the electrode reaction by switching the polarity of the electrode at one time interval of 1 second or more and 20 seconds or less as one electrode and using the same or different conductive material as the other electrode, the general formula

[0042]

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(Wherein 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) and a general formula

[0044]

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(Wherein, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group) and a general formula

[0046]

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Si—Si comprising a structural unit represented by
A method for producing a network polymer having a bond as a skeleton.

5. The method for producing a network-like polymer having a Si-Si bond as a skeleton according to any one of claims 1 to 4, wherein the electrode reaction is performed under irradiation of ultrasonic waves.

In the following, the inventions of the above-mentioned items 1 to 4 are referred to as the first to fourth inventions of the present application, and when these are summarized, they are simply referred to as the present invention.

In the first invention of the present application, the compound used as a starting material has the general formula

[0051]

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

[0053]

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(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 about 1 to 10 carbon atoms, and among them, those having 1 to 6 carbon atoms are more preferable. As the aryl group, a phenyl group, a carbon atom 1
A substituted phenyl group, a p-alkoxyphenyl group, a naphthyl group, etc., having at least one of the above-mentioned alkyl groups as substituents. Examples of the alkoxy group include those having about 1 to 10 carbon atoms, and among them, those having 1 to 6 carbon atoms are more preferable. When R is an amino group or an organic substituent described above, at least one of its 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). As the halogen atom, Cl is more preferable.

In the trihalosilane represented by the general formula (2), examples of the alkyl group include those having about 1 to 10 carbon atoms, and among them, those having 1 to 6 carbon atoms are more preferable. Examples of the aryl group include a phenyl group, a substituted phenyl group having at least one kind of an alkyl group having 1 to 6 carbon atoms as a substituent, a p-alkoxyphenyl group, and a naphthyl group. Examples of the alkoxy group include those having about 1 to 10 carbon atoms, and among them, those having 1 to 6 carbon atoms are more preferable. When R is an amino group or an organic substituent described above, at least one of its hydrogen atoms is still another alkyl group or aryl group. It may be substituted by a functional group such as an alkoxy group.

In the first invention of the present application, one or more compounds represented by the general formula (1) and the compound represented by the general formula (2)
And at least one compound represented by the formula: It is preferable that these compounds have as high a purity as possible. For example, it is preferable to use them by distillation before use.

The reaction product obtained in the first invention of the present application has the general formula

[0060]

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(Wherein R is the same as above and two R
May be the same or different. ) And the general formula

[0062]

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(Wherein R is the same as described above), and is a network polymer having a skeleton of a Si—Si bond composed of a structural unit represented by the following formula:

In the reaction of the first invention of the present application, the compound represented by the general formula (1) and the compound represented by the general formula (2) are dissolved in a solvent and used. The mixing ratio of both compounds is compound (1): compound (2) = 1000: 1.
It is preferably in the range of 50,000 to 50,000. In the case of this mixing ratio, the mixture is soluble in an organic solvent, and the resulting polymer exerts a composite function having both properties of a linear polysilane and a network polymer, which is preferable. is there.

As the solvent, aprotic solvents can be widely used, and more specifically, tetrahydrofuran, 1,1,
Examples thereof include 2-dimethoxyethane, bis (2-methoxyethyl) ether, p-dioxane, propylene carbonate, acetonitrile, dimethylformamide, dimethylsulfoxide, and methylene chloride. These solvents can be used alone or as a mixture of two or more. As the solvent, it is more preferable to use an ether-based solvent such as tetrahydrofuran, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, p-dioxane alone or as a mixture with another solvent.
Particularly preferred solvents are tetrahydrofuran and 1,2
-Dimethoxyethane. If the concentration of the mixture of the compound (1) and the compound (2) in the solvent is too low, the current efficiency will decrease, whereas if it is too high, the supporting electrolyte may not be dissolved. Therefore, the concentration of the raw material mixture in the solvent is usually about 0.05 to 20 mol / l, more preferably about 0.1 to 15 mol / l, and particularly preferably about 0.2 to 13 mol / l. .

The supporting electrolyte used in the present invention includes 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. Among these supporting electrolytes, lithium perchlorate and tetra-n-butylammonium perchlorate are more preferable, and lithium perchlorate is most preferable. When the concentration of the supporting electrolyte is too low, the reaction does not proceed sufficiently due to the low ionic conductivity given to the reaction solution, whereas when the concentration is too high, the current flows too much and is necessary for the reaction. No potential is 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. It 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 as the cathode, the same or different conductive preparation (Ni, Co, Pt, etc.) is used. When both electrodes are made of the same material, metal ions (eg, Mg ²⁺ ) are eluted and moved between the two electrodes, so that the electrodes are less consumed and the energization time is longer. This is preferable for synthesizing a high molecular weight network polymer. The material of both electrodes is M
g, Al or an alloy mainly containing these metals is more preferable, and Mg is most preferable. The shape of the electrode is not particularly limited as long as the current can be supplied stably, but is preferably a rod-like, plate-like, tubular-like, or a plate-like body wound in a coil shape. It is preferable to remove the oxide film from the surface of the electrode as much as possible in advance. The removal of the oxide film from the electrode may be performed by any method, for example, after washing the electrode with an acid, washing with ethanol and ether, drying under reduced pressure, and polishing the electrode under a nitrogen atmosphere. It can be performed by a method or a method combining these methods.

In carrying out the first invention of the present application, a mixture of the compounds represented by the general formulas (1) and (2) and a supporting electrolyte are accommodated together with a solvent in a sealable reaction vessel provided with an anode and a cathode. The electrode reacts by passing a predetermined amount of current while switching the polarity of the electrode while stirring mechanically or magnetically. The polarity is switched at intervals of about 1 to 20 seconds in order to realize a strong reduction system. Inside the reaction vessel,
A dry atmosphere may be used, 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 electric current may be generally 1 F / mol or more based on the halogen atoms in the raw material mixture, and the molecular weight can be controlled by adjusting the amount of electric current. It is also possible to take out the reticulated polymer produced at an amount of electricity of about 0.1 F / mol or more out of the system, recover the remaining raw material halosilane, and reuse it. The temperature during the reaction may be within a temperature range not higher than the boiling point of the solvent used. 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 network polymer, and the like. In the first invention of the present application, it is not necessary to use a diaphragm which is indispensable in the ordinary electrode reduction reaction, and the operation is simplified and advantageous.

In the second invention of the present application, the compound used as a starting material has the general formula

[0070]

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

[0072]

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(Wherein X is as defined above).

In the tetrahalosilane represented by the general formula (5), Cl is more preferable as the halogen atom.

The second invention of the present application uses, as a starting material, a mixture of one or more of the compounds represented by the general formula (1) and one or more of the compounds represented by the general formula (5). There is no difference from the first invention of the present application in the reaction conditions and the like except for the point. However, the mixing ratio of both compounds is as follows: compound (1): compound (5) = 1000:
It is preferred to be in the range of 1 to 1000.

The reaction product obtained in the second invention of the present application has the general formula

[0077]

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(Wherein R is the same as above and two R
May be the same or different. ) And the general formula

[0079]

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Si—Si comprising a structural unit represented by
It is a network polymer having a bond as a skeleton.

In the third invention of the present application, the compound used as a starting material has the general formula

[0082]

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

[0084]

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(Wherein, X is as defined above).

The third invention of the present application is characterized in that one or more of the compounds represented by the general formula (2) and one or more of the compounds represented by the general formula (5) are used as starting materials. In terms of the reaction conditions,
There is nothing different from the invention. However, the mixing ratio of both compounds is compound (2): compound (5) = 1000: 1 to 10
It is preferable to set the range to 0.

The reaction product obtained by the third invention of the present application has the general formula

[0088]

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

[0090]

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Si—Si comprising a structural unit represented by
It is a network polymer having a bond as a skeleton.

The fourth invention of the present application is characterized in that, as starting materials, one or more of the compounds represented by the general formula (1) and one or more of the compounds represented by the general formula (2) and the general formula (5) Except for using a mixture of one or more of the compounds represented by the formula (1), there is no difference from the first invention of the present application in reaction conditions and the like. However, the mixing ratio of each compound is as follows: compound (1): compound (2): compound (5) = 1000: 0.5-800: 0.5-10
It is preferable to set the range to 0.

The reaction product obtained in the fourth invention of the present application has the general formula

[0094]

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

[0096]

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

[0098]

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Si—Si comprising a structural unit represented by
It is a network polymer having a bond as a skeleton.

In the present invention, ultrasonic waves can be applied to the reaction vessel or the reaction solution during the electrode reaction. The method of irradiating the ultrasonic wave during the electrode reaction is not particularly limited, but a method of irradiating the reactor with the ultrasonic bath contained therein, and a method of irradiating the reactor with an ultrasonic oscillator inserted therein. And the like. The ultrasonic frequency is 10
The frequency is preferably set to about 70 kHz. The output of the ultrasonic wave may be appropriately determined according to the reaction conditions such as the type of the raw material, the amount of the reaction solution, the shape and size of the reaction vessel and the electrode, the material and the surface area of the electrode. It is in the range of about 0.01 to 24 kW. By such ultrasonic irradiation, the reaction time is greatly shortened to about 1/3 to 2/3 of the case where no ultrasonic irradiation is performed, and the molecular weight is increased and the yield is remarkably improved. In the present invention, stirring is preferably performed by ultrasonic irradiation, but if necessary, stirring by mechanical means may be further used.

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

The average molecular weight of the network polymer having a Si—Si bond as a skeleton obtained by the present invention is usually 1000
About 1,000,000.

[0103]

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

(A) Since no alkali metal is used, Si—Si can easily and safely be produced even on an industrial scale.
A network polymer having a bond as a skeleton can be produced.

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

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

(D) The formation of Si—O—Si bonds in the skeleton can be greatly suppressed. (E) Since the use of a diaphragm is not required, the operation is simple without clogging of the diaphragm.

(F) When ultrasonic irradiation is performed during the electrode reaction, the reaction time is greatly reduced to about 2/3 to 1/3, the molecular weight of the reaction product is increased, and the yield is increased. Significant improvement.

[0109]

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

Example 1 A three-way cock and a Mg electrode (1 cm × 1 cm × 5 cm; the surface was washed with dilute sulfuric acid, washed with ethanol and ether, dried under reduced pressure, polished under a nitrogen atmosphere, and oxidized on the surface) 3 with an inner volume of 30ml
A 1-necked flask (hereinafter referred to as a reactor) was charged with 1 g of anhydrous lithium perchlorate, and heated at 50 ° C. and 1 mmHg to reduce the pressure (6).
Time), after drying lithium perchlorate, deoxygenated dry nitrogen was introduced into the reactor, and tetrahydrofuran 15 previously dried with sodium-benzophenone ketyl was added.
ml was added. To this, 1.45 ml of methylphenyldichlorosilane and 0.16 ml of phenyltrichlorosilane which had been distilled in advance were added, and while the reactor was kept at room temperature by a water bath, electricity was supplied from a constant voltage power supply. At this time, using a commutator, the polarity of the two electrodes was changed every 15 seconds, and 2 F / mo was determined based on chlorine in the monomer.
The current was supplied for 35 hours so that the amount of current supplied became l.

After completion of the reaction, the resultant was reprecipitated with poor solvent ethanol and good solvent benzene. As a result, a polymer having a weight average molecular weight of 9970 was obtained in a yield of 65% as a network polymer having a Si-Si bond as a skeleton.

As a result of elemental analysis, it was confirmed that the oxygen content in this polymer was 0.1% or less, and the content of Si—O—Si was extremely low.

Example 2 An electrode reaction was carried out in the same manner as in Example 1 except that the amount of tetrahydrofuran used was changed to 7.5 ml.

As a result, S having a weight average molecular weight of 13500
A network polymer having an i-Si bond as a skeleton has a yield of 52
%.

Example 3 An electrode reaction was carried out in the same manner as in Example 1 except that the reactor was immersed in an ultrasonic cleaner having an output of 60 W and a frequency of 45 KHz to carry out the reaction.

As a result, S having a weight average molecular weight of 12200
A network polymer having an i-Si bond as a skeleton has a yield of 87.
%.

Example 4 An electrode reaction was carried out in the same manner as in Example 1 except that one electrode was formed of Mg and the other electrode was formed of Ni. A network having the same Si-Si bond as a skeleton was obtained. A polymer was obtained.

Example 5 An electrode reaction was carried out in the same manner as in Example 1 except that both electrodes were made of Cu. As a result, a network polymer having the same Si-Si bond as a skeleton was obtained.

Example 6 An electrode reaction was carried out in the same manner as in Example 1 except that both electrodes were made of Al. As a result, a network polymer having the same skeleton of Si-Si bonds was obtained.

Example 7 An electrode reaction was carried out in the same manner as in Example 1 except that 3 g of tetra-n-butylammonium perchlorate was used as a supporting electrolyte.
A network polymer having a Si bond as a skeleton was obtained at a yield of 53%.

Example 8 An electrode reaction was carried out in the same manner as in Example 1 except that 1,2-dimethoxyethane was used as a solvent. As a result, a network polymer having a weight average molecular weight of 6,300 and having a Si-Si bond as a skeleton was obtained. Obtained at a rate of 60%.

Example 9 1.13 ml of predistilled methylphenyldichlorosilane and 0.48 ml of phenyltrichlorosilane as starting materials
The electrode reaction was carried out in the same manner as in Example 1 except that the polymer was used. As a result, a network polymer having a weight average molecular weight of 10600 and having a skeleton of a Si—Si bond was obtained at a yield of 62%.

Example 10 0.81 ml of predistilled methylphenyldichlorosilane and 0.80 ml of phenyltrichlorosilane as raw materials
Was performed in the same manner as in Example 1 except that the polymer was used. As a result, a network polymer having a weight average molecular weight of 4960 and having a Si-Si bond as a skeleton was obtained at a yield of 63%.

Example 11 0.48 ml of predistilled methylphenyldichlorosilane and 1.12 ml of phenyltrichlorosilane as raw materials
The electrode reaction was carried out in the same manner as in Example 1 except that the polymer was used. As a result, a network polymer having a weight average molecular weight of 6,720 and having a Si-Si bond as a skeleton was obtained at a yield of 70%.

Example 12 The amount of electricity was 1 F / mo based on the chlorine component in the raw material mixture.
An electrode reaction was carried out in the same manner as in Example 1 except for changing to l.

As a result, Si with a weight average molecular weight of 4530
A network polymer having a skeleton of -Si bond was obtained at a yield of 51%.

Example 13 An electrode reaction was carried out in the same manner as in Example 1 except that methyl-p-biphenyldichlorosilane was used as dichlorosilane.

As a result, a network polymer having a corresponding Si—Si bond as a skeleton was obtained. Example 14 An electrode reaction was carried out in the same manner as in Example 10 except that 1.0 ml of methyl-n-hexyldichlorosilane was used as dichlorosilane.

As a result, S having a weight average molecular weight of 17450
28% yield of network polymer with i-Si bond as skeleton
Was obtained.

Example 15 An electrode reaction was carried out in the same manner as in Example 14 except that 0.99 ml of n-hexyltrichlorosilane was used as trichlorosilane.

As a result, S having a weight average molecular weight of 12,500
11% yield of a network polymer having an i-Si bond as a skeleton
Was obtained.

Example 16 An electrode reaction was carried out in the same manner as in Example 3 except that 1.13 ml of methylphenyldichlorosilane and 0.34 ml of tetrachlorosilane distilled in advance were used as raw materials. A network polymer having a Si bond as a skeleton was obtained at a yield of 41%.

Example 17 An electrode reaction was carried out in the same manner as in Example 3 except that 1.0 ml of methylphenyldichlorosilane and 0.57 ml of tetrachlorosilane were used.
A network polymer having a skeleton of 80 Si-Si bonds was obtained in a yield of 18%.

Example 18 Phenyltrichlorosilane previously distilled as a raw material
The electrode reaction was carried out in the same manner as in Example 3 except that 60 ml and 0.06 ml of tetrachlorosilane were used. As a result, a network polymer having a weight average molecular weight of 8,380 and having a skeleton of a Si-Si bond was obtained at a yield of 31%. Was.

Example 19 An electrode reaction was carried out in the same manner as in Example 18 except that 1.98 ml of n-hexyltrichlorosilane was used as trichlorosilane.

As a result, S having a weight average molecular weight of 13900
17% yield of network polymer having i-Si bond as skeleton
Was obtained.

Example 20 An electrode reaction was carried out in the same manner as in Example 1 except that a raw material mixture consisting of 1.61 ml of methylphenyldichlorosilane, 0.16 ml of phenyltrichlorosilane and 0.11 ml of tetrachlorosilane was used.

As a result, S having a weight average molecular weight of 11300
54% yield of network polymer having i-Si bond as skeleton
Was obtained.

Reference Example 1 FIG. 1 shows the results of thermogravimetric analysis of the network polymer having the skeleton of the Si—Si bond obtained in Example 1.

FIG. 2 shows the results of thermogravimetric analysis of a conventional linear polysilane having a Si-Si bond as a 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 apparent.

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 of the network polymer having the skeleton of the Si—Si bond obtained in Example 1.

From the comparison of FIG. 3 to FIG.
It is clear that the network polymer having a -Si bond as a skeleton has the optical properties of both polysilane and silicon network polymer.

[Brief description of the drawings]

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

──────────────────────────────────────────────────続 き Continuing on the front page (72) Ryoichi Nishida, Inventor Osaka Gas Co., Ltd. 4-1-2, Hiranocho, Chuo-ku, Osaka-shi (72) Inventor Shinichi Kawasaki 4-chome, Hiranocho, Chuo-ku, Osaka-shi, Osaka No. 1-2, Osaka Gas Co., Ltd. (56) References JP-A-2-105825 (JP, A) JP-A-62-241926 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) C08G 77/60

Claims (5)

(57) [Claims] 1. A method for producing a network polymer having a Si--Si bond as a skeleton, comprising a general formula: (Wherein, 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 and general formula (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 a perchlorate is used as a supporting electrolyte. Using an aprotic solvent as a solvent, Mg, Cu or Al as one pole,
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 a time interval of 1 second or more and 20 seconds or less, the 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.) And a general formula: ] (Wherein, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group.) A method for producing a network polymer having a skeleton of a Si—Si bond composed of a structural unit represented by the following formula: 2. A method for producing a network polymer having a Si--Si bond as a skeleton, comprising a general formula: (Wherein, 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 and general formula (Wherein X represents a halogen atom), a perchlorate is used as a supporting electrolyte, an aprotic solvent is used as a solvent, and Mg, Cu
Alternatively, Al is used as one electrode, and the same or different conductive material is used as the other electrode and subjected to an electrode reaction in which the polarity of the electrode is switched at a time interval of 1 second or more and 20 seconds or less. ] (Wherein R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group, and the two Rs may be the same or different) and a general formula: ] A method for producing a network polymer having a skeleton of a Si-Si bond composed of a structural unit represented by the formula: 3. A method for producing a network polymer having a Si--Si bond as a skeleton, comprising a general formula: (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 a general formula: (Where X represents a halogen atom), a perchlorate is used as a supporting electrolyte, an aprotic solvent is used as a solvent, and Mg, Cu
Alternatively, Al is used as one electrode, and the same or different conductive material is used as the other electrode, and subjected to an electrode reaction in which the polarity of the electrode is switched at a time interval of 1 second or more and 20 seconds or less. ] (Wherein, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group) and a general formula: A method for producing a network polymer having a skeleton of a Si—Si bond composed of a structural unit represented by the formula: 4. A method for producing a network polymer having a Si-Si bond as a skeleton, comprising a general formula: (Wherein, 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 and general formula (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 a trihalosilane represented by the general formula: (Where X represents a halogen atom), a perchlorate is used as a supporting electrolyte, an aprotic solvent is used as a solvent, and Mg, Cu
Alternatively, Al is used as one electrode, and the same or different conductive material is used as the other electrode and subjected to an electrode reaction in which the polarity of the electrode is switched at a time interval of 1 second or more and 20 seconds or less. ] (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.) And a general formula: ] (Wherein, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or an amino group) and a general formula: A method for producing a network polymer having a skeleton of a Si-Si bond composed of a structural unit represented by the formula: 5. The method for producing a network polymer having a Si-Si bond as a skeleton according to claim 1, wherein the electrode reaction is performed under irradiation of ultrasonic waves.