JPH07316303A - Production of network-like polymer containing si-si bond as skeleton - Google Patents

Abstract

PURPOSE:To obtain a network-like polymer having Si-Si bond as a skeleton in a high yield and high operability by subjecting a dihalosilane to electrode reaction under specific conditions to form a linear polysilane, adding a trihalosilane, etc., to a reactional system containing the formed linear polysilane and further subject the mixture to an electrode reaction. CONSTITUTION:A dihalosilane of formula I [(m) is 1-3; each R is independently H, an alkyl, an aryl, etc.; X is a halogen] is subjected to an electrode reaction using Mg or Mg-based alloy as anode, Li salt as a supporting electrolyte and an aprotic solvent as a solvent, respectively. A trihalosilane of the formula RSiX3 and/or a tetrahalosilane of the formula SiX4 are directly added to a reaction system containing the produced linear polysilane having a halogen at both ends of a compound of formula II [(n) is 10-1000] and the mixture is subjected to the electrode reaction. Thereby, the objective polymer composed of a structural unit of formula III and a structural unit of the formula RSiidentical and/or a structural unit of the formula IV, having a narrow molecular weight distribution and useful as a ceramics precursor, optical and electronic materials, etc., is obtained.

Description

Detailed Description 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 has excellent heat resistance stability similar to that of a silicon network polymer, and has a composite property that has the properties of both materials such that it has the same performance as polysilane in terms of optical and electronic functions. It has a function.

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 within 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 is possible.

As such a method, an electrode reaction using a dihalosilane as a raw material, using a metal such as Mg as an electrode, using lithium perchlorate as a supporting electrolyte, and using tetrahydrofuran (THF) as a solvent After producing a linear polysilane having halogen atoms at both ends and having a degree of polymerization in a certain range, at least one of trihalosilane and tetrahalosilane is added to the same reaction system, followed by electrode reaction. Go to the desired Si
A method for producing a network polymer having a —Si bond as a skeleton has been proposed (JP-A-5-230218).

This method uses a safe metal for the anode and provides an active electrode reduction system, and there is no danger of environmental pollution, the operability is good, the yield is high, and the molecular weight is uniform. It has an advantage that a network polymer having a Si-Si bond as a skeleton can be produced. However, in this method, a perchlorate such as lithium perchlorate used as a supporting electrolyte is expensive, and care must be taken when handling it. Therefore, the supporting electrolyte is inexpensive and easy to handle. There was a demand for the emergence of a new reaction system using.

[0006]

Therefore, the main object of the present invention is to produce a network polymer having a uniform molecular weight and having a skeleton of Si-Si bond as a skeleton in a high yield, with good operability, safely and inexpensively. It is to provide a new method that can be done.

[0007]

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 found that dihalosilane is used as a positive electrode of a specific metal and a specific solvent and a specific supporting electrolyte. First, a linear polysilane having halogen atoms at both ends and having a certain degree of polymerization is produced by subjecting it to an electrode reaction, and then at least one of trihalosilane and tetrahalosilane is added to the same reaction system. However, it has been found that when the electrode reaction is continued, the problems of the prior art are substantially eliminated or significantly reduced.

Further, when a specific chemical substance is added to the reaction system as a current-carrying aid, the current-carrying property is greatly improved,
It has been found that the time required to produce polysilane is significantly reduced.

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:

[0010]

[Chemical 15]

(In the formula, m is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group. When m = 1, two R's represent m = 2. 4 Rs in the case of, and 6 Rs in the case of m = 3 may be the same or different in two or more:
X represents a halogen atom), and the dihalosilane represented by the general formula is used in an electrode reaction using Mg or a Mg-based alloy as an anode, a Li salt as a supporting electrolyte, and an aprotic solvent as a solvent.

[0012]

[Chemical 16]

Forming a linear polysilane having halogens at both ends, wherein R and X are the same as above corresponding to the starting materials: n is 10 to 1000; and (b ) A general formula for a reaction system containing the above linear polysilane represented by the general formula (2)

[0014]

[Chemical 17]

(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 general formula

[0016]

[Chemical 18]

A tetrahalosilane represented by the formula (wherein X represents a halogen atom) is added as it is and subjected to an electrode reaction to give a compound of the general formula

[0018]

[Chemical 19]

(Wherein R and n are the same as above corresponding to the starting materials) and the general formula

[0020]

[Chemical 20]

(Wherein R is the same as above corresponding to the starting material) and / or the general formula

[0022]

[Chemical 21]

Si-Si consisting of the structural unit represented by
A method comprising the step of forming a network polymer having a bond as a skeleton.

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

[0025]

[Chemical formula 22]

(In the formula, m is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group. When m = 1, two R's represent m = 2. 4 Rs in the case of, and 6 Rs in the case of m = 3 may be the same or different in two or more:
X represents a halogen atom), a dihalosilane represented by Mg or a Mg-based alloy is used as an anode, a Li salt is used as a supporting electrolyte, and an Al salt, Fe salt, Mg salt, Zn salt, Sn salt, Co are used.
By using a salt, a Pd salt, a V salt, a Cu salt, or a Ca salt as an energization aid and subjecting it to an electrode reaction using an aprotic solvent as a solvent, a compound of the general formula

[0027]

[Chemical formula 23]

Forming a linear polysilane having halogens at both ends, wherein R and X are the same as above corresponding to the starting materials: n is 10 to 1000; and (b ) A general formula for a reaction system containing the above linear polysilane represented by the general formula (2)

[0029]

[Chemical formula 24]

(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 general formula

[0031]

[Chemical 25]

A tetrahalosilane represented by the formula (wherein X represents a halogen atom) is added as it is and subjected to an electrode reaction to give a compound of the general formula

[0033]

[Chemical formula 26]

(Wherein R and n are the same as above corresponding to the starting materials) and the general formula

[0035]

[Chemical 27]

(Wherein R is the same as above corresponding to the starting material) and / or the general formula

[0037]

[Chemical 28]

Si-Si consisting of the structural unit represented by
A method comprising the step of forming a network polymer having a bond as a skeleton.

3. Item 3. The method according to Item 1 or 2, wherein LiCl is used as the supporting electrolyte.

4. AlCl ₃ , FeC as an energization aid
4. The method according to item 2 or 3 above, wherein l ₂ , FeCl ₃ , CoCl ₂ or CuCl ₂ is used.

Hereinafter, the "inventions described in claims 1 and 2" are referred to as the first invention and the second invention of the present application, respectively, and both inventions are collectively referred to as the present invention.

1. First invention of the present application In the step (a) of the first invention of the present application, the dihalosilane used as a starting material has the general formula

[0043]

[Chemical 29]

(In the formula, m is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group. When m = 1, two R's represent m = 4 Rs in the case of 2 and 6 Rs in the case of m = 3 may be the same or different in two or more: X represents a halogen atom).

In the dihalosilane represented by the general formula (1), m is 1 to 3, and the hydrogen atom, amino group and organic substituent (alkyl group, aryl group, alkoxy group, amino group) represented by R are , Each may be the same, and two or more may be different from each other. More specifically, two Rs are provided when m = 1 and four Rs are provided when m = 2.
When one R is m = 3, the six Rs may be the same or two or more may be different.

As the compound represented by the general formula (1),
More preferably, m is 1 or 2. Examples of the alkyl group include those having about 1 to 10 carbon atoms, and among these, those having 1 to 6 carbon atoms are more preferable. Examples of the aryl group include a phenyl group, a phenyl group having one or more alkyl groups 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 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 substituted with another functional group such as an alkyl group, an aryl group or an alkoxy group. Examples of such a functional group include those similar to the above.

Further, 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 kind of the dihalosilane represented by the general formula (1) may be used alone, or two kinds thereof may be used in combination. The dihalosilane is preferably as pure as possible. For example, liquid dihalosilane is preferably used after being dried by calcium hydride and distilled, and solid dihalosilane is used by a recrystallization method. It is preferably purified, and used.

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

[0050]

[Chemical 30]

(Wherein R and X are as defined above,
Two Rs may be the same or different. )
Is 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 dihalosilane represented by the general formula (1) is dissolved in a solvent and used.

As the solvent, aprotic solvents can be widely used, and more specifically, tetrahydrofuran, 1,2
Examples thereof include ether solvents such as dimethoxyethane, propylene carbonate, acetonitrile, dimethylformamide, dimethylsulfoxide, bis (2-methoxyethyl) ether, p-dioxane, and methylene chloride. These solvents can be used alone or as a mixture of two or more kinds. Tetrahydrofuran and 1,2-dimethoxyethane are more preferable as the solvent.
If the concentration of dihalosilane 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 dihalosilane in the solvent is usually about 0.05 to 20 mol / l, more preferably about 0.2 to 15 mol / l, and particularly preferably about 0.3 to 13 mol / l.

Examples of the supporting electrolyte used in the step (a) of the first invention of the present application include inexpensive lithium salts such as LiCl, LiNO ₃ and Li ₂ CO ₃ . These supporting electrolytes may be used alone or in combination of two or more kinds. Among these supporting electrolytes, LiCl is most preferable.

If the concentration of the supporting electrolyte is too low,
Whereas if the current is too high, the amount of reduced and precipitated lithium is too large and the desired product, the linear polysilane, Si-Si The main chain bond is cleaved and its molecular weight is reduced. Therefore, the concentration of the supporting electrolyte in the solvent is usually 0.0
5 to 5 mol / l, more preferably 0.1 to 5 mol / l.
It is about 3 mol / l, and particularly preferably 0.15 to
It is about 2.0 mol / l.

In the step (a) of the first invention of the present application, Mg or an alloy containing Mg as a main component is used as the anode. As an alloy containing Mg as a main component, for example, Al is 3
The thing containing about 10% is mentioned. Also, JIS
1 type (MG 6125-1961)
A1), 2 types (MGA2, commonly known as AZ63), 3 types (MG
A3) etc. are mentioned. The cathode is not particularly limited as long as it can pass an electric current, but SUS304, 3
Stainless steel such as 16; Mg, Cu, Zn, Sn, A
Examples include various metals such as 1, Ni, and Co; carbon materials and the like. The shape of the electrode is not particularly limited as long as it can stably conduct electricity, but a rod, a plate, a cylinder, a cone, a disc, a spherical body or pellets housed in a basket,
A plate-shaped body wound in a coil shape is preferable. If necessary, the oxide film on the electrode surface is removed in advance. The oxide film can be removed from the electrode by any method. For example, the electrode is washed with an 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.

The step (a) of the first invention of the present application includes, for example,
(I) A dihalosilane represented by the general formula (1) and a supporting electrolyte are housed together with a solvent in a hermetically sealed reaction vessel equipped with an anode and a cathode, preferably with a predetermined amount of current while mechanically or magnetically stirring. (Ii) charging into a reaction solution storage tank using a flow-type electrode reaction apparatus composed of an electrolytic cell equipped with an anode and a cathode, a reaction solution storage tank, a pump, piping, etc. The reaction solution consisting of the dihalosilane, the supporting electrolyte, and the solvent is circulated in the electrode reaction apparatus by a pump, and a predetermined amount of current is passed through the electrode reaction apparatus to carry out the electrode reaction in the electrolytic cell.

The structure or shape of the electrolytic cell is not particularly limited, but a structure of a type that easily replenishes the anode which is dissolved and consumed in the reaction solution as the reaction proceeds can be used. More specifically, for example, as shown in a schematic perspective view in FIG. 1, an electrolytic cell of a type in which a consumable anode is continuously supplied by a small spherical body or pellet 3 housed in a basket or a basket-like container 1. You can do it. Alternatively,
As shown in FIG. 2, according to the "pencil sharpening type electrolytic cell" disclosed in JP-A-62-56589, an electrolysis of a type in which a metal or alloy noblock 7 serving as an anode is laminated in a cathode sheet 5. It may be used as a tank. When an anode of the type shown in FIG. 1 is used, as shown in FIG. 3, a basket 1 containing a spherical body 3 of a metal or an alloy is placed in a cathode 21 which also serves as an outer wall of an electrolytic cell 23, and electrolysis is performed. Perform the reaction.

When an electrolytic cell equipped with such a continuous supply type anode is used, it is not necessary to replace the consumable electrode once or every several reactions, so that a long-term repetitive reaction becomes possible. The cost required for replacing the anode is reduced, and the production cost of the polymer is reduced.

The inside of the reaction vessel or reactor may be a dry atmosphere, but a dry nitrogen or inert gas atmosphere is more preferable, and a deoxygenated and dry nitrogen atmosphere or an inert gas atmosphere is more preferable. Is particularly preferred. The energization amount may be about 1 F / mol or more based on the halogen in dihalosilane, and the molecular weight can be controlled by adjusting the energization amount. The reaction time may differ depending on the amount of the starting dihalosilane, the resistance of the electrolytic solution related to the amount of the supporting electrolyte, and the like, and thus may be appropriately determined. The temperature during the reaction is usually in the temperature range from -20 ° C to the boiling point of the solvent used, more preferably in the range of about -5 to 30 ° C, and most preferably 0 to.
Within the range of about 25 ° C. Step (a) of the first invention of the present application
In, in the usual electrode reduction reaction, the diaphragm which is essential, may be used, but since it is not essential,
The operation is simple and practically 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.

[0062]

[Chemical 31]

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

[0064]

[Chemical 32]

A tetrahalosilane represented by the formula (where X is the same as above) is directly added, and the same electrode reaction as that described above is continued to give a compound of the general formula

[0066]

[Chemical 33]

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

[0068]

[Chemical 34]

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

[0070]

[Chemical 35]

And a structural unit represented by
A network polymer having a unit as a skeleton is produced.

The mixing ratio of compound (3) and / or compound (4) in step (b) of the first invention of the present application is preferably as follows.

(A) When only compound (3) is added, compound (1): compound (3) = 1000: 1 to 50
It is preferably within the range of 00.

(A) When only compound (4) is added, compound (1): compound (4) = 1000: 1 to 10
It is preferably within the range of 00.

(C) When the compound (3) and the compound (4) are added, compound (1): compound (3): compound (4) = 1000: 0.5 to 800: 0.5 to 100
It is preferably within the range.

In the case of such a mixing ratio, the mixture is soluble in an organic solvent, and the polymer produced has a property of both a linear polysilane and a network silicon network polymer. It is suitable because it exerts various functions.

The reaction conditions in the step (b) of the first invention of the present application are not substantially different from the reaction conditions in the step (a).

The network polymer obtained in the step (b) of the first invention of the present application may vary depending on the kind of raw materials, reaction conditions and the like, but usually has an average molecular weight of 2000 to 100000.
It is about 0.

2. Second Invention of the Present Application The second invention of the present application is, in order to perform the electrode reaction of the present invention more efficiently, in combination with a supporting electrolyte in addition to a current-carrying auxiliary agent, in order to improve the current-carrying property. There is no substantial difference from the first invention.

As the current-carrying aid, AlCl ₃ , Al (O
Al salt such as Et) ₃ ; F such as FeCl ₂ and FeCl ₃
e salt; Mg salt such as MgCl ₂ ; Zn such as ZnCl ₂
Salt; Sn salt such as SnCl ₂ ; Co salt such as CoCl ₂ ;
Pd salt such as PdCl ₂ ; V salt such as VCl ₃ ; CuCl
Cu salts such as ₂ ; Ca salts such as CaCl ₂ are exemplified as preferable ones. These energization aids may be used alone or in combination of two or more. Among these energization aids, AlCl ₃ , FeCl ₂ , FeCl ₃ ,
CoCl ₂ , CuCl _{2 and the} like are more preferable. If the concentration of the current-carrying aid in the solvent is too low, improvement of the current-carrying property is not sufficiently achieved, while if it is too high, the current-carrying aid is reduced and does not participate in the reaction. Therefore, the concentration of the energization aid in the solvent is usually about 0.01 to 6 mol / l, more preferably about 0.03 to 4 mol / l, and particularly preferably about 0.05 to 3 mol / l. is there. By adding such a current-carrying aid, the reaction time is greatly shortened, and efficient production of polysilane becomes possible.
The degree of shortening of the reaction time varies depending on the concentration of the current-carrying aid, the concentrations of the supporting electrolyte and the starting dihalosilane, etc., but is usually about 1/4 to 3/4 of that when the current-carrying aid is not used.

The reticulated polymer obtained in the second invention of the present application may also vary depending on the type of raw material, reaction conditions, etc., but the average molecular weight is usually about 2000 to 1,000,000.

[0082]

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

(A) A reticulated polymer having a Si-Si bond as a skeleton can be produced in high yield.

(B) Since an expensive supporting electrolyte is not used,
A network polymer having a Si-Si bond as a skeleton can be manufactured at low cost.

(C) Care must be taken in handling Since a supporting electrolyte is not used, a network polymer having a Si-Si bond as a skeleton can be easily produced at low cost.

(D) When an energization aid is used, the electroconductivity is better, so that the reaction time is about 1/4 to 3/4 as compared with the case where the energization aid is not used. And a network polymer having a Si—Si bond as a skeleton can be efficiently produced.

(E) When AlCl ₃ or the like is used as the energization aid, it is not necessary to neutralize the reaction solution after completion of the reaction, so that the post-treatment is extremely simple.

[0088]

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

Example 1 Step (a) Three-way cock and Mg anode (diameter 1 cm × 5 cm) and stainless steel (SUS304) cathode (1 cm × 1)
cm 3 × 5 cm) equipped with a 30-ml internal volume three-necked flask (hereinafter referred to as a reactor) anhydrous lithium chloride (LiC
l) 0.4 g was housed, the pressure was reduced to 1 mmHg at 50 ° C., LiCl was dried, deoxygenated dry nitrogen was introduced into the reactor, and further 15 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl was added. added. 0.96 g (5 mmol) of methylphenyldichlorosilane purified by distillation in advance was added to this with a syringe, and while stirring the reaction solution with a magnetic stirrer, while keeping the reactor at room temperature with a water bath, electricity was supplied with a constant voltage power source. . Electric current is 1.0 F / based on the chlorine atom in methylphenyldichlorosilane.
It was carried out for about 18 hours so that the energization amount was mol.

A portion of the product was taken and analyzed,
It was confirmed that a linear polysilane having a weight average molecular weight of 8700 (average degree of polymerization of about 72) was produced.

Step (b) Next, 1.06 g (5 mmol) of phenyltrichlorosilane was introduced into the above reactor, and 1.3 F / mol based on the chlorine atom in phenyltrichlorosilane.
The electricity was applied for 12 hours so that the amount of electricity was equal to.

After completion of the reaction, 20 ml of 1N hydrochloric acid was added to the reaction solution.
Then, 80 ml of distilled water was added, and ether 10 was added.
It was extracted with 0 ml and reprecipitated with 80 ml of poor solvent ethanol and 4 ml of good solvent tetrahydrofuran.

As a result, S having a weight average molecular weight of 20100 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 62.
Obtained at 0%.

Example 2 The amount of phenylmethyldichlorosilane used in step (a) was 1.34 g (7 mmol), and the amount of phenyltrichlorosilane used in step (b) was 0.63 g (3 m).
mol), and the electrode reaction was carried out in the same manner as in Example 1.

As a result, S having a weight average molecular weight of 24200 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 52.
Obtained at 0%.

Example 3 The amount of phenylmethyldichlorosilane used in step (a) was 0.57 g (3 mmol), and the amount of phenyltrichlorosilane used in step (b) was 1.48 g (7 m).
mol), and the electrode reaction was carried out in the same manner as in Example 1.

As a result, S having a weight average molecular weight of 18500 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 68.
Obtained at 5%.

Example 4 Same as Example 1 except that 0.99 g (5 mmol) of cyclohexylmethyldichlorosilane purified by a distillation method was used as the starting dihalosilane represented by the general formula (1) used in step (a). Then, the electrode reaction was carried out. .

After completion of the reaction, 20 ml of 1N hydrochloric acid was added to the reaction solution.
80 ml of distilled water was added, and hexane 10 was added.
It was extracted with 0 ml and reprecipitated using 80 ml of a poor solvent acetone and 4 ml of a good solvent hexane.

As a result, S having a weight average molecular weight of 31300 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 71.
Obtained at 1%.

Example 5 The same as Example 1 except that 0.73 g (5 mmol) of methylmethoxydichlorosilane purified by a distillation method was used as the starting dihalosilane represented by the general formula (1) used in step (a). Then, the electrode reaction was carried out.

As a result, Si having a weight average molecular weight of 7,200 was obtained.
The yield of the network polymer having a —Si bond as a skeleton is 39.5.
Obtained in%.

Example 6 Example 6 was repeated except that 1.03 g (5 mmol) of p-anisylmethyldichlorosilane purified by a distillation method was used as the starting dihalosilane represented by the general formula (1) used in step (a). An electrode reaction was performed in the same manner as in 1.

As a result, S having a weight average molecular weight of 23,800 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 59.
Obtained in 8%.

Example 7 As the starting dihalosilane represented by the general formula (1) used in the step (a), 1,2-dichloro-purified by a distillation method was used.
1,1,2-Trimethyl-2-phenylsilane 1.25
An electrode reaction was carried out in the same manner as in Example 1 except that g (5 mmol) was used.

As a result, S having a weight average molecular weight of 18700 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 41.
Obtained at 2%.

Example 8 Example 8 was repeated except that 1.19 g (5 mmol) of phenethyltrichlorosilane purified by a distillation method was used as the raw material represented by the general formula (3) used in the step (b). Electrode reaction was carried out.

As a result, S having a weight average molecular weight of 22300 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 62.
Obtained at 2%.

Example 9 In the same manner as in Example 1 except that 1.09 g (5 mmol) of cyclohexyltrichlorosilane purified by a distillation method was used as the raw material represented by the general formula (3) used in the step (b). Electrode reaction was carried out.

After completion of the reaction, 20 ml of 1N hydrochloric acid was added to the reaction solution.
80 ml of distilled water was added, and hexane 10 was added.
It was extracted with 0 ml and reprecipitated using 80 ml of a poor solvent acetone and 4 ml of a good solvent hexane.

As a result, S having a weight average molecular weight of 25900 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 59.
Obtained in 9%.

Example 10 The amount of phenylmethyldichlorosilane used in step (a) was 1.91 g (10 mmol), and 0.09 g (0.5) of tetrachlorosilane purified by the distillation method in step (b).
The electrode reaction was performed in the same manner as in Example 1 except that (mmol) was used.

As a result, S having a weight average molecular weight of 21100 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 32.
Obtained at 0%.

Example 11 Cyclohexylmethyldichlorosilane 0.9 purified by a distillation method as the starting dihalosilane in step (a)
Using 9 g (5 mmol), as a raw material in step (b), cyclohexyltrichlorosilane 1.09 g (5
The electrode reaction was performed in the same manner as in Example 1 except that (mmol) was used.

After completion of the reaction, 20 ml of 1N hydrochloric acid was added to the reaction solution.
80 ml of distilled water was added, and hexane 10 was added.
It was extracted with 0 ml and reprecipitated using 80 ml of a poor solvent acetone and 4 ml of a good solvent hexane.

As a result, S having a weight average molecular weight of 35900 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 65.
Obtained in 3%.

Example 12 1.40 g (5 mmol) of phenylmethyldibromosilane was used as the starting dihalosilane in step (a) and 1.73 g (5 mmol) of phenyltribromosilane was used as the starting material in step (b). Electrode reaction was carried out in the same manner as in Example 1.

As a result, S having a weight average molecular weight of 17500 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 54.
Obtained in 6%.

Example 13 Mg alloy (Mg 90%, Al 9%, Zn 1
%: 1 cm × 1 cm × 5 cm), an electrode reaction was carried out in the same manner as in Example 1, and as a result, a yield of a network polymer having a weight average molecular weight of 21700 and having a Si—Si bond as a skeleton was 53. It was obtained at 0.3%.

Example 14 A Mg alloy (Mg 95.5%, Al 3%, Zn
The electrode reaction was performed in the same manner as in Example 1 except that 1%, Mn 0.5%, 1 cm × 1 cm × 5 cm) was used.

As a result, S having a weight average molecular weight of 21600 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 56.
Obtained in 9%.

Example 15 Glassy carbon (1 cm × 0.1 cm ×) as a cathode
The electrode reaction was carried out in the same manner as in Example 1 except that 5 cm) was used.

As a result, S having a weight average molecular weight of 19,500 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 60.
Obtained in 7%.

Example 16 An electrode reaction was carried out in the same manner as in Example 1 except that 0.65 g of LiNO ₃ was used as a supporting electrolyte.

As a result, a network polymer having a high molecular weight Si--Si bond as a skeleton was obtained in good yield.

Example 17 An electrode reaction was carried out in the same manner as in Example 1 except that 0.70 g of Li ₂ CO ₃ was used as the supporting electrolyte.

As a result, a network polymer having a high molecular weight Si-Si bond as a skeleton was obtained in good yield.

Example 18 Step (a) Three-way cock and Mg anode (diameter 1 cm × 5 cm) and stainless steel (SUS304) cathode (1 cm × 1)
(cm × 5 cm) equipped with a three-necked flask (hereinafter referred to as a reactor) having an internal volume of 30 ml, 0.4 g of anhydrous lithium chloride (LiCl) as a supporting electrolyte and 0.25 g of anhydrous aluminum chloride (AlCl ₃ ) as an energization aid. Housing
LiCl and A under reduced pressure by heating to 50 ° C. and 1 mmHg
After drying 1Cl ₃ , deoxygenated dry nitrogen was introduced into the reactor, and further 15 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl was added. 0.96 g (5 mmol) of methylphenyldichlorosilane purified by distillation in advance was added to this with a syringe, and the reaction solution was stirred with a magnetic stirrer,
While the reactor was kept at room temperature with a water bath, electricity was supplied with a constant voltage power source. The energization was performed for about 5 hours so that the energization amount was 1.0 F / mol based on the chlorine atom in methylphenyldichlorosilane.

A part of the product was collected and analyzed,
It was confirmed that a linear polysilane having a weight average molecular weight of 9100 (average degree of polymerization: about 76) was formed.

Step (b) Next, 1.06 g (5 mmol) of phenyltrichlorosilane was introduced into the above reactor, and 1.3 F / mol based on the chlorine atom in phenyltrichlorosilane.
The current was applied for about 7 hours so that the amount of current applied was about 7 hours.

After the reaction was completed, 100 ml of distilled water was added to the reaction solution.
Was added, and the mixture was extracted with 100 ml of ether and reprecipitated using 80 ml of a poor solvent ethanol and 4 ml of a good solvent tetrahydrofuran.

As a result, S having a weight average molecular weight of 29,700 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 66.
Obtained in 3%.

Example 19 An electrode reaction was carried out in the same manner as in Example 18 except that the amount of LiCl used was 0.8 g. In this case, the energization time required in the step (a) was about 4 hours, and the energization time required in the step (b) was about 5 hours.

As a result, S having a weight average molecular weight of 27100 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 62.
Obtained at 2%.

Example 20 An electrode reaction was carried out in the same manner as in Example 18 except that the amount of AlCl ₃ as a current carrying aid was changed to 0.13 g. In this case, the energization time required in the step (a) was about 6 hours, and the energization time required in the step (b) was about 8 hours.

As a result, S having a weight average molecular weight of 30100 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 64.
Obtained at 5%.

Example 21 An electrode reaction was carried out in the same manner as in Example 18 except that 0.18 g of MgCl ₂ was used as a current carrying aid.

As a result, a network polymer having a high molecular weight Si-Si bond as a skeleton was obtained in good yield.

Example 22 An electrode reaction was conducted in the same manner as in Example 18 except that 0.26 g of ZnCl ₂ was used as a current carrying aid.

As a result, a network polymer having a high molecular weight Si-Si bond as a skeleton was obtained in good yield.

Example 23 An electrode reaction was carried out in the same manner as in Example 18 except that 0.52 g of CaCl ₂ was used as a current carrying aid.

As a result, a network polymer having a high molecular weight Si-Si bond as a skeleton was obtained in good yield.

Example 24 An electrode reaction was carried out in the same manner as in Example 18 except that 15 ml of DME previously dried with sodium-benzophenone ketyl was used as a solvent.

As a result, S having a weight average molecular weight of 18900 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 48.
Obtained at 2%.

Example 25 Step (a) Mg anode (12 cm × 15 cm × 1 cm) and stainless steel cathode (SUS316, 12 cm × 15 cm ×)
1 cm) mounted filter press type electrolytic cell (distance between electrodes 5 mm), reaction solution storage tank of 3000 ml capacity, bellows type pump and piping.
₃ accommodates 17g, dry nitrogen was deoxygenated was introduced into the reactor, further pre sodium - tetrahydrofuran was added 1000ml drying with benzophenone ketyl. To this, 64 g (0.33 mol) of methylphenyldichlorosilane, which had been purified by distillation in advance, was added with a syringe, and while the reaction solution was circulated by a bellows type pump (the linear velocity when passing between the electrodes was 20 cm / sec), the cooler While keeping the reaction temperature at room temperature by means of, a current was supplied by a constant voltage power source. The energization was carried out for about 9 hours at 1.0 F / mol based on the chlorine atom in methylphenyldichlorosilane.

A part of the product was collected and analyzed,
It was confirmed that a linear polysilane having a weight average molecular weight of 5200 (average degree of polymerization: about 43) was formed.

Step (b) Next, phenyltrichlorosilane 7 was placed in the reactor described above.
0 g (0.33 mol) was introduced, and electricity was supplied for 19 hours so that the amount of electricity was 1.3 F / mol based on the chlorine atom in phenyltrichlorosilane.

After completion of the reaction, the reaction solution was added with distilled water (1000 m).
1, and extracted with 1500 ml of ether, 2000 ml of poor solvent ethanol, 50 m of good solvent tetrahydrofuran
It was reprecipitated using 1.

As a result, S having a weight average molecular weight of 30100 was obtained.
The yield of the network polymer having an i-Si bond as a skeleton is 59.
Obtained in 3%.

Example 26 An electrode reaction was carried out in the same manner as in Example 18 except that 0.24 g of FeCl ₂ was used as a current carrying aid. As a result, a network polymer having a weight average molecular weight of 39,600 and having a Si—Si bond as a skeleton was obtained at a yield of 69.3%.

Example 27 An electrode reaction was carried out in the same manner as in Example 18 except that 0.31 g of FeCl ₃ was used as a current carrying aid. As a result, a network polymer having a weight average molecular weight of 23100 and having a Si—Si bond as a skeleton was obtained at a yield of 41.2%.

Example 28 An electrode reaction was carried out in the same manner as in Example 18 except that 0.49 g of SnCl ₂ was used as a current carrying aid. As a result, a network polymer having a weight average molecular weight of 13200 and having a Si—Si bond as a skeleton was obtained at a yield of 49.3%.

Example 29 An electrode reaction was carried out in the same manner as in Example 18 except that 0.24 g of CoCl ₂ was used as a current carrying aid. As a result, a network polymer having a weight average molecular weight of 19,300 and having a Si—Si bond as a skeleton was obtained at a yield of 60.2%.

Example 30 An electrode reaction was carried out in the same manner as in Example 18 except that 0.33 g of PdCl ₂ was used as a current carrying aid. As a result, a network polymer having a weight average molecular weight of 13900 and having a Si—Si bond as a skeleton was obtained at a yield of 22.7%.

Example 31 An electrode reaction was carried out in the same manner as in Example 18 except that 0.29 g of VCl ₃ was used as a current carrying aid. as a result,
A network polymer having a weight average molecular weight of 18,800 and having a Si—Si bond as a skeleton was obtained at a yield of 23.2%.

Example 32 An electrode reaction was carried out in the same manner as in Example 18 except that 0.25 g of CuCl ₂ was used as a current carrying aid. As a result, a network polymer having a weight average molecular weight of 20100 and having a Si—Si bond as a skeleton was obtained at a yield of 39.1%.

[Brief description of drawings]

FIG. 1 is a perspective view showing the outline of the method of the present invention in which a spherical body of a metal or an alloy forming an anode is housed in a cage or a basket and used.

FIG. 2 is a schematic cross-sectional view showing an outline when a pencil sharpening type electrolytic cell is used as an electrolytic cell used for carrying out the method of the present invention.

FIG. 3 is a schematic cross-sectional view showing an outline of an electrolytic cell using an anode of the type shown in FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Basket-like container or basket 3 ... Metal spherical body or pellets 5 ... Cathode 7 ... Block-shaped anode 21 ... Cathode 23 ... Electrolyzer

Claims (4)

[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, m is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group.
Two Rs when m = 1, four Rs when m = 2, and six Rs when m = 3 may be the same or different from each other: X represents a halogen atom) and dihalosilane represented by Mg or M
By subjecting the g-based alloy as an anode, Li salt as a supporting electrolyte and an aprotic solvent as a solvent to an electrode reaction, a compound of the general formula: Where R and X are the same as above corresponding to the starting materials:
(n is 10 to 1000), and 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) are generally used. Formula [3] (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: By adding a tetrahalosilane represented by the formula (X represents a halogen atom) as it is and subjecting it to an electrode reaction, a compound of the general formula: (Wherein R and n are the same as above corresponding to the starting materials) and a general formula: (Wherein R is the same as above corresponding to the starting material) and / or the general formula: And a step of forming a reticulated polymer having a Si—Si bond as a skeleton, which comprises a structural unit represented by 2. A method for producing a network polymer having a Si—Si bond as a skeleton, which comprises (a) a general formula: (In the formula, m is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group.
Two Rs when m = 1, four Rs when m = 2, and six Rs when m = 3 may be the same or different from each other: X represents a halogen atom) and dihalosilane represented by Mg or M
g-based alloy as anode, Li salt as supporting electrolyte, Al
Salt, Fe salt, Mg salt, Zn salt, Sn salt, Co salt, Pd
A salt, a V salt, a Cu salt, or a Ca salt is used as an energization aid and is subjected to an electrode reaction using an aprotic solvent as a solvent to give a compound of the general formula Where R and X are the same as above corresponding to the starting materials:
(n is 10 to 1000), and 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) are generally used. 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 / or a general formula: A tetrahalosilane represented by the formula (X represents a halogen atom) is added as it is and subjected to an electrode reaction to give a compound represented by the general formula: (Wherein R and n are the same as above corresponding to the starting materials) and the general formula: (Where R is the same as above corresponding to the starting material) and / or the general formula And a step of forming a reticulated polymer having a Si—Si bond as a skeleton, which comprises a structural unit represented by 3. The method according to claim 1, wherein LiCl is used as the supporting electrolyte. 4. AlCl ₃ , FeCl ₂ , as an energization aid,
The method according to claim ₂ or ₃ , wherein FeCl ₃ , CoCl ₂ or CuCl ₂ is used.