JP3089333B2 - Method for producing silane germane copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a silane germane copolymer.

[0002]

2. Description of the Related Art Silane-germane copolymers are expected to be useful as optical and electronic materials.

Conventionally, as a method for producing a silane-germane copolymer, organodichlorosilane and organodichlorogermane in a toluene solvent are stirred for a long time at a temperature of 100 ° C. or higher using an alkali metal such as sodium metal to form a reductive product. Is known. ｛J. Polym. Sci .: Polymer Chemistry, Ed., 23 (1985) 2099-
2107｝. However, this method requires harsh reaction conditions (for example, prolonged heating, etc.), has a low material yield, cannot control the molecular weight of the product, and is not suitable for production on an industrial scale. However, since a large amount of alkali metal is used, there are major problems such as lack of safety.

[0004]

Accordingly, the present invention provides a novel process for producing a silane-germane copolymer which is excellent in safety, has a high material yield, and can control the molecular weight of the product, even when produced on an industrial scale. Its main purpose is to provide a method.

[0005]

Means for Solving the Problems The present inventor has conducted intensive studies in view of the state of the prior art as described above. As a result, the specific halosilane and halogermane are used as anodes and specific metals are used as supporting electrolytes. When subjected to an electrode reaction using perchlorate, a polymerization reaction at normal temperature becomes possible,
It has been found that the yield is increased and the problems of the prior art are substantially eliminated or greatly reduced.

It has also been found that in such an electrode reaction, when the reaction is performed by switching the polarity of both electrodes, the efficiency of the reaction is greatly improved.

Further, it has been found that when the reactor or the reaction solution is irradiated with ultrasonic waves during the electrode reaction as described above, the reaction time is greatly reduced and the yield is improved.

That is, the present invention provides the following method for producing a silane-germane copolymer: A process for producing a silane germane copolymer, comprising:

[0009]

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(Where a is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X represents a halogen atom; a = 1 In the case of, two Rs may be the same or different. When a = 2, the four Rs may be the same or two or more may be different.
In the case of 3, 6 Rs may be the same or 2
One or more may be different. ) And the general formula

[0011]

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(Where b is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X represents a halogen atom; b = 1 In the case of, two Rs may be the same or different, and when b = 2, four Rs may be the same or two or more may be different, and b =
In the case of 3, 6 Rs may be the same or 2
One or more may be different. An electrode using perchlorate as a supporting electrolyte, using an aprotic solvent as a solvent, and using Mg, Cu or Al as an anode, with or without irradiation of halogermane represented by By subjecting to the reaction, the general formula

[0013]

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Wherein R is the same as above, depending on the starting materials; m and n are each 2 to 11000.

2. A process for producing a silane germane copolymer, comprising:

[0016]

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(Where a is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X represents a halogen atom; a = 1 In the case of, two Rs may be the same or different. When a = 2, the four Rs may be the same or two or more may be different.
In the case of 3, 6 Rs may be the same or 2
One or more may be different. ) And the general formula

[0018]

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(Where b is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X represents a halogen atom; b = 1 In the case of, two Rs may be the same or different, and when b = 2, four Rs may be the same or two or more may be different, and b =
In the case of 3, 6 Rs may be the same or 2
One or more may be different. ) And with halogermane under or without ultrasonic irradiation, using perchlorate as a supporting electrolyte, using an aprotic solvent as a solvent, and using Mg, Cu or Al as one pole,
By subjecting the same type or different types of conductive materials to the other electrode and performing an electrode reaction in which the polarity of the electrode is switched at regular time intervals, the general formula

[0020]

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Wherein R is the same as above, depending on the starting material; m and n are each 2 to 11000.

3. Item 3. The method according to Item 2, wherein the switching of the electrode polarity is performed at an arbitrary time interval.

In the following, the invention described in the above item 1 is referred to as the first invention of the present application, and the invention described in the above item 2 is referred to as the second invention of the present application.
The invention is simply referred to as the present invention when these are summarized. Item 3 will be described in relation to the second invention of the present application.

In the present invention, the compound used as one of the starting materials has the general formula

[0025]

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(Where a is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X represents a halogen atom). Halosilane.

In the present invention, the compound used as the other starting material is a compound represented by the general formula:

[0028]

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(Wherein b is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X represents a halogen atom). Halo Germanic. A method for producing such a halogermane is described in, for example, a method for producing a compound in which a = 1, R = n-hexyl, and X = a chlorine atom is described in J. Poly. S.
Ci .: Poly. Chem. Ed. Vol. 25, 111-25 (1987). Further, other compounds can be produced by the same method. In addition, such a halogermane is used for a nucleophilic substitution reaction with a Grignard reagent (J. Am. Che.
m. Soc. Vol. 82, 3016-18 (1960)).

The reaction product in the present invention has the general formula

[0031]

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(Wherein R is the same as above depending on the starting material; m and n are each about 2 to 11,000).

In the halosilane represented by the general formula (1), R may be different from each other or may be the same. More specifically, when a = 1, two Rs may be the same or different, and when a = 2, four Rs may be the same or 2
May be different from each other, and when a = 3, 6
R may be the same, or two or more may be different. As the compound represented by the general formula (1), a compound in which a = 1 is more preferable. 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 substituted phenyl group having at least one kind of an alkyl group having 1 to 6 carbon atoms as a substituent,
p-Alkoxyphenyl group, naphthyl group and the like. 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 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 halogermane represented by the general formula (2), R may be different from each other or may be the same. More specifically, b =
In the case of 1, two Rs may be the same or different, and in the case of b = 2, the four Rs may be the same or two or more may be different, and b = 3 In this case, each of the six Rs may be the same or two.
One or more may be different. As the compound represented by the general formula (2), a compound in which b = 1 is more preferable.
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. The alkoxy group may have 1 to 1 carbon atoms.
And about 0, and among them, carbon number of 1 to 6
Are more preferred. When R is an amino group or an organic substituent described above, at least one of its hydrogen atoms may be substituted with another functional group such as an alkyl group, an aryl group, or an alkoxy group.

In the general formula (2), X represents a halogen atom (Cl, F, Br, I). As the halogen atom, Cl is more preferable.

In the method of the present invention, one or more of the compounds included in the general formula (1) and one or more of the compounds included in the general formula (2) can be used. .

The halosilane and halogermane are preferably as pure as possible. For example, it is preferable to distill before use.

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 ratio of the compound (1) to the compound (2) is about compound (1): compound (2) = 1: 0.01 to 100.

As the solvent to be used, 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. As the solvent, tetrahydrofuran and 1,2-dimethoxyethane are more preferred. If the concentration of the raw material in the solvent is too low, the current efficiency is reduced, while 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 3 mol / l, more preferably about 0.1 to 1.5 mol / l, and particularly preferably 0.2 to 0.5 mol / l. It is about l.

The supporting electrolyte used in the present invention includes alkali metal perchlorates such as sodium perchlorate and lithium perchlorate; and tetraalkyl ammonium perchlorates such as tetra-n-butylammonium perchlorate. Chlorate. These supporting electrolytes may be used alone or in combination of two or more. Among these supporting electrolytes, 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 0.3 to 1 mol / l. .

In the first invention of the present application, as the anode, M
One of g, Cu, and Al or an alloy mainly containing these metals is used, and the same or different conductive material (Ni, Co, Pt, etc.) is used as the cathode. As the anode material, Mg, 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, the halosilane, halogermane and the supporting electrolyte represented by the general formulas (1) and (2) are accommodated together with a solvent in a hermetically sealable reaction vessel provided with both electrodes, By conducting a predetermined amount of current while stirring magnetically or magnetically, an electrode reaction is performed. The inside of the reaction vessel may be a dry atmosphere, but more preferably a dry nitrogen or inert gas atmosphere, and most preferably a deoxygenated and dry nitrogen or inert gas atmosphere. The amount of electricity may be generally about 1 F / mol or more based on the halogen atoms in the raw material, and the molecular weight can be controlled by adjusting the amount of electricity. Also, 0.1
It is also possible to take out the silane-germane copolymer produced with an amount of electricity of about F / mol or more out of the system, collect the remaining raw materials, and reuse them. The reaction time varies depending on the amounts of the raw material halosilane and halogermane, the resistance of the electrolytic solution related to the amount of the supporting electrolyte, the desired molecular weight of the silanegermane copolymer, and the like, and may be appropriately determined as necessary.

In the first aspect of the present invention, ultrasonic waves may be applied to the reaction vessel or the reaction solution in order to shorten the reaction time. 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 frequency of the ultrasonic wave is 1
It is preferable to set it to about 0 to 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. The reaction time is greatly shortened by such ultrasonic irradiation,
When the ultrasonic wave is not irradiated, the molecular weight is reduced to about 1/3 to 2/3, the molecular weight is increased, and the yield is improved.

In the first invention of the present application, the temperature during the reaction may be within a temperature range not higher than the boiling point of the solvent used. One of the great advantages of the present invention is that the reaction can be carried out even near room temperature.

In the first invention of the present application, it is not necessary to use a diaphragm which is indispensable in a normal electrode reduction reaction, and the operation is simplified and advantageous.

The second invention of the present application is substantially the same as the first invention of the present application except that the polarities of the two electrodes are switched at fixed time intervals. The polarity switching is usually performed at intervals of about 1 second to 10 minutes, more preferably at intervals of about 10 seconds to 3 minutes. By performing this polarity switching, the efficiency of the reaction is greatly improved in that the reaction time is shortened. In addition, when both electrodes are made of the same material, the consumption of the electrodes is reduced, which is preferable.

The switching of the polarity of the electrode during the reaction may be performed at an arbitrary time interval. That is, 1
The polarity of the electrode can be switched at any time interval within the range of seconds to 10 minutes. For example, the time interval of polarity switching can be shortened or extended as the reaction proceeds. This change of the time interval can be performed regularly or randomly.

In the present invention, in order to suppress a side reaction of the halosilane represented by the general formula (1) and the halogermane represented by the general formula (2) with water, water in the solvent and the supporting electrolyte is removed in advance. It is desirable to keep. For example, tetrahydrofuran or 1,
In the case of using 2-dimethoxyethane, it is preferable to perform drying with sodium-benzophenone ketyl or the like in advance. 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.

[0050]

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

(A) Since the reaction can be carried out under mild conditions and no alkali metal is used, the operability and safety are excellent even in industrial scale production, while avoiding the risk of environmental pollution. To produce silane-germane copolymers.

(B) A silane-germane copolymer can be synthesized with a better yield than the conventional method.

(C) By adjusting the amount of current, etc.,
The molecular weight of the resulting silane-germane copolymer can be controlled (in the general formula (3), n = 2 to 110)
00).

(D) An oxygen atom insertion reaction into the polymer main chain such as a Si—O—Si bond 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 waves are applied during the electrode reaction, the reaction time can be greatly reduced to about 1/2.

[0057]

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 hydrochloric acid, washed with ethanol and acetone, dried under reduced pressure, polished under a nitrogen atmosphere, and oxidized on the surface. 3) with an internal volume of 30 ml
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. 1g of methylphenyldichlorosilane
And 1.5 g of butylphenyldichlorogermane were added. The reactor was immersed in an ultrasonic cleaner having an output of 60 W and a frequency of 45 KHz. The reactor was kept at room temperature by a cooler, and was powered by 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 / mol based on chlorine in methylphenyldichlorosilane and butylphenyldichlorogermane.
For 18 hours.

After the reaction was completed, the reaction solution was added to 80 ml of 1N hydrochloric acid, extracted with ether, and then reprecipitated with poor solvent ethanol and good solvent benzene.

As a result, a silane germane copolymer having a weight average molecular weight of 105,000 was obtained in a yield of 33%.

Example 2 An electrode reaction was carried out for 42 hours in the same manner as in Example 1 except that the polarities of the two electrodes were not switched.

As a result, a silane germane copolymer having a weight average molecular weight of 76,000 was obtained at a yield of 17%.

Example 3 An electrode reaction was carried out in the same manner as in Example 1 except that 1 g of dibutyldichlorogermane was used as a raw material represented by the general formula (2). As a result, a silane germane copolymer having a weight average molecular weight of 1150 was obtained.

Example 4 An electrode reaction was carried out in the same manner as in Example 1 except that Mg (1 cm × 1 cm × 5 cm) was used as an anode and Ni (1 cm × 0.1 cm × 5 cm) was used as a cathode. As a result, a silane germane copolymer having a weight average molecular weight of 31,000 was obtained at a yield of 15%.

Example 5 An electrode reaction was carried out in the same manner as in Example 1 except that two electrodes were made of Al (1 cm × 0.1 cm × 5 cm).
As a result, a silane germane copolymer having a weight average molecular weight of 6,800 was obtained at a yield of 9%.

Example 6 An electrode reaction was carried out in the same manner as in Example 1 except that tetra-n-butylammonium perchlorate was used as a supporting electrolyte. As a result, a silane germane copolymer having a weight average molecular weight of 10,500 was obtained at a yield of 10%.

Example 7 An electrode reaction was carried out in the same manner as in Example 1 except that 15 ml of 1,2-dimethoxyethane previously dried with sodium-benzophenone ketyl was used as a solvent. As a result, a silane germane copolymer having a weight average molecular weight of 57000 was obtained at a yield of 29%.

Example 8 An electrode reaction was carried out for 41 hours in the same manner as in Example 1 except that no ultrasonic wave was applied. As a result, a silane germane copolymer having a weight average molecular weight of 39000 was obtained at a yield of 2
Obtained at 2%.

Example 9 An electrode reaction was performed for 60 hours in the same manner as in Example 1 except that no ultrasonic wave was applied and the polarities of the two electrodes were not changed. As a result, a silane germane copolymer having a weight average molecular weight of 10,500 was obtained at a yield of 11%.

Example 10 An electrode reaction was carried out in the same manner as in Example 1 except that 1,2-dichlorophenyltrimethyldisilane was used as a starting compound represented by the general formula (1). As a result, a corresponding silane germane copolymer having a weight average molecular weight of 12,000 was obtained in a yield of 16%.

Example 11 An electrode reaction was carried out in the same manner as in Example 1 except that 1,2-dichlorophenyltrimethyldigemane was used as a starting compound represented by the general formula (2). As a result, a corresponding silane-germane copolymer having a weight average molecular weight of 9800 was obtained in a yield of 13%.

Example 12 Example 12 was repeated except that 2,2-diphenyl-1,1,3,3-tetramethyl-1,3-dichlorotrisilane was used as a starting compound represented by the general formula (1). An electrode reaction was performed in the same manner. As a result, a weight average molecular weight of 140
00 corresponding silane-germane copolymer yield 15%
Was obtained.

Example 13 Example 13 was repeated except that 2,2-diphenyl-1,1,3,3-tetramethyl-1,3-dichlorotrigermane was used as a starting compound represented by the general formula (2). An electrode reaction was performed in the same manner. As a result, the weight average molecular weight 11
2,000 corresponding silane-germane copolymers with a yield of 12
%.

Example 14 The electrode reaction was carried out in the same manner as in Example 1 except that the time interval of the polarity conversion of the electrode by the commutator was 1 minute and the subsequent time interval was 15 seconds until the amount of electricity passed was 1 F / mol. Done. The energization time was about 20 hours.

As a result, a corresponding silane-germane copolymer having a weight average molecular weight of 88,000 was obtained in a yield of 29%.

──────────────────────────────────────────────────続 き Continued on the front page (72) Ryoichi Nishida, Inventor Osaka Gas Co., Ltd. 4-1-2, Hirano-cho, Chuo-ku, Osaka-shi, Osaka (72) Inventor Hiroaki Murase 4-chome, Hirano-cho, Chuo-ku, Osaka-shi, Osaka No. 1-2 Osaka Gas Co., Ltd. (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 79/00

Claims (3)

(57) [Claims] 1. A process for producing a silane-germane copolymer, comprising the general formula: (Where a is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X represents a halogen atom; when a = 1, Is such that two Rs may be the same or different, and a =
In the case of 2, four Rs may be the same or 2
May be different from each other, and when a = 3, 6
R may be the same or two or more may be different. ) And a general formula: (Where b is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X represents a halogen atom; and when b = 1, Is such that two Rs may be the same or different and b =
In the case of 2, four Rs may be the same or 2
May be different from each other, and when b = 3, 6
R may be the same or two or more may be different. ) With or without irradiation with ultrasonic waves, using perchlorate as a supporting electrolyte, using an aprotic solvent as a solvent,
By subjecting it to an electrode reaction using g, Cu or Al as the anode, the general formula (Wherein R is the same as above depending on the starting material; m and n are each 2 to 11000). 2. A method for producing a silane-germane copolymer, comprising the general formula: (Where a is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X represents a halogen atom; when a = 1, Is such that two Rs may be the same or different, and a =
In the case of 2, four Rs may be the same or 2
May be different from each other, and when a = 3, 6
R may be the same or two or more may be different. ) And a general formula: (Where b is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group; X represents a halogen atom; and when b = 1, Is such that two Rs may be the same or different and b =
In the case of 2, four Rs may be the same or 2
May be different from each other, and when b = 3, 6
R may be the same or two or more may be different. ) With or without irradiation with ultrasonic waves, using perchlorate as a supporting electrolyte, using an aprotic solvent as a solvent,
g, Cu or Al is used as one of the electrodes, and the same or different conductive material is used as the other electrode to perform an electrode reaction in which the polarity of the electrode is switched at regular time intervals. (Wherein R is the same as above depending on the starting material; m and n are each 2 to 11000). 3. The method according to claim 2, wherein the switching of the polarity of the electrode is performed at an arbitrary time interval.