JPH05163354A - Preparation of organopolygermane - Google Patents
Preparation of organopolygermaneInfo
- Publication number
- JPH05163354A JPH05163354A JP35099791A JP35099791A JPH05163354A JP H05163354 A JPH05163354 A JP H05163354A JP 35099791 A JP35099791 A JP 35099791A JP 35099791 A JP35099791 A JP 35099791A JP H05163354 A JPH05163354 A JP H05163354A
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- Prior art keywords
- group
- formula
- substituted
- organic
- polygermane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
【０００１】[0001]
【技術分野】本発明は、導電性材料、フォトレジスト、
重合開始剤、セラミックス前駆体、電子写真感光体、キ
ャリア移動剤などとして有用な有機ポリゲルマンの新規
な製造法に関する。TECHNICAL FIELD The present invention relates to a conductive material, a photoresist,
The present invention relates to a novel method for producing an organic polygermane which is useful as a polymerization initiator, a ceramics precursor, an electrophotographic photoreceptor, a carrier transfer agent and the like.
【０００２】[0002]
【従来技術】従来、有機ポリゲルマンの製造法として
は、有機ゲルマニウムジハロゲン化物を出発原料として
アルカリ金属等で脱ハロゲン化縮合する方法が知られて
いる（たとえば、M.Lesbre，P.Mazerolles，J.Satge，
“The Organic Compound of Germanium”John Wiley ＆
Sons (1971）や藤野、特開平１−２５２６３７号公報
参照）。2. Description of the Related Art Conventionally, as a method for producing organic polygermane, a method of dehalogenating and condensing an organic germanium dihalide as a starting material with an alkali metal or the like is known (for example, M. Lesbre, P. Mazerolles, J. .Satge,
“The Organic Compound of Germanium” John Wiley &
Sons (1971) and Fujino, JP-A-1-252637).
【化３】 ここで、Ａ、Ｂは有機置換基、Ｘはハロゲン原子、Ｍは
アルカリ金属、ｚは１０〜１０００である。一般式(II
I）の反応はウルツ型反応であり、反応の初期にナトリ
ウムからのゲルマニウムへの電子移動によって、ハロゲ
ン化ゲルマンのアニオンラジカルが発生し、続いて生成
する種々のゲルマニウム中間体（例えば、ゲルミルラジ
カル、ゲルミルアニオン、ゲルミレン、ゲルミレンアニ
オン、ゲルメン等）を経由して有機ポリゲルマンが生成
すると考えられている。このようにして製造された有機
ポリゲルマンの分子量分布はバイモーダル（ｂｉｍｏｄ
ａｌ）分布といわれる２つの幅広いピークを示す。この
ように従来の製造法が複数のピークをもつ分子量分布を
もつポリマーを与える理由はあきらかではないが、有機
ポリシランの製造においても同様な分布を示すことか
ら、アルカリ金属を用いた縮重合にみられる特有の現象
と考えられる。したがって、前述のような製造法は、こ
のように複数のピークの分子量分布をもつポリマーしか
得られず、かつ収量が低いなど多くの欠点をかかえてい
る。[Chemical 3] Here, A and B are organic substituents, X is a halogen atom, M is an alkali metal, and z is 10 to 1000. General formula (II
The reaction of I) is a wurtz-type reaction, in which the anion radical of germane halide is generated by the electron transfer from sodium to germanium in the initial stage of the reaction, and then various germanium intermediates (for example, germanyl radical) are generated. , Germanyl anion, germylene, germylene anion, germene, etc.), and organic polygermane is considered to be produced. The molecular weight distribution of the organic polygermane produced in this way is bimodal.
al) shows two broad peaks called distribution. Thus, the reason why the conventional production method gives a polymer having a molecular weight distribution having a plurality of peaks is not clear, but the similar distribution is shown in the production of organic polysilane. It is considered to be a unique phenomenon. Therefore, the above-mentioned production method has many drawbacks such that only a polymer having a molecular weight distribution of a plurality of peaks can be obtained and the yield is low.
【０００３】[0003]
【目的】本発明の目的は、単一のピークの分子量分布を
もつ有機ポリゲルマンを、高収率で得ることができる製
造法を提供することにある。[Object] It is an object of the present invention to provide a method for producing an organic polygermane having a single peak molecular weight distribution in a high yield.
【０００４】[0004]
【構成】本発明は、次式（Ｉ）The present invention has the following formula (I)
【化４】 （式中、Ｒ1およびＲ2は、互いに同一または相異なって
いてもよく、水素原子、炭素数１〜２０のアルキル基、
置換または無置換芳香族基、および置換または無置換脂
環族基よりなる群から選ばれるものである。但し、アル
キル基は互いに結合しＧｅ原子と一緒にＧｅ含有環を形
成することもできる。また、Ｒ3は芳香族置換基を表わ
す。）で示されるジゲルモキサンに光照射させることを
特徴とする、次式（II）[Chemical 4] (In the formula, R1And R2Are the same or different from each other
May be a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
Substituted or unsubstituted aromatic group, and substituted or unsubstituted fat
It is selected from the group consisting of cyclic groups. However,
Kill groups are linked together to form a Ge-containing ring with a Ge atom.
It can also be done. Also, R3Represents an aromatic substituent
You ) Digermoxane
Characteristic, the following formula (II)
【化５】 （式中、Ｒ1およびＲ2は、前記に同じ。）で示される繰
り返し単位よりなる有機ポリゲルマンの製法に関する。[Chemical 5] (In the formula, R1And R2Is the same as above. )
The present invention relates to a method for producing an organic polygermane composed of repeating units.
【０００５】本発明の製法は、例えば前記式（I）のジ
ゲルモキサンを有機溶媒に溶解し、該溶液に光照射する
ことによって行われる。The production method of the present invention is carried out, for example, by dissolving the digermoxane of the above formula (I) in an organic solvent and irradiating the solution with light.
【０００６】該製法に使用される有機溶媒としては、ジ
エチルエーテル、テトラヒドロフランなどのエーテル
系、ペンタン、ヘキサン、シクロヘキサンなどの炭化水
素系あるいはベンゼン、トルエンなどの芳香族炭化水素
系などが使用できる。反応を行うに際しては、これら有
機溶媒はあらかじめ乾燥して使用することが好ましい。
また、光照射を行う際の光源としては、低圧水銀灯、中
圧水銀灯、高圧水銀灯、超高圧水銀灯、レーザー、キセ
ノンランプなどを使用することができる。さらに、反応
温度は、−８０℃から１２０℃の範囲で行うことができ
る。いずれの反応においても、空気中の酸素との反応を
避けるために不活性ガス下でおこなうのが好ましい。As the organic solvent used in the production method, an ether type solvent such as diethyl ether and tetrahydrofuran, a hydrocarbon type solvent such as pentane, hexane and cyclohexane, or an aromatic hydrocarbon type solvent such as benzene and toluene can be used. When carrying out the reaction, it is preferable to dry these organic solvents in advance before use.
As a light source for light irradiation, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a laser, a xenon lamp, etc. can be used. Further, the reaction temperature may be in the range of -80 ° C to 120 ° C. In any reaction, it is preferable to carry out under an inert gas in order to avoid reaction with oxygen in the air.
【０００７】前記一般式（Ｉ）および（II）中、置換基
Ｒ1からＲ3としては、メチル基、エチル基、ｎ−プロピ
ル基、ｉ−プロピル基、ｎ−ブチル基、ｓ−ブチル基、
ｔ−ブチル基、ｎ−ペンチル基、ｉ−ペンチル基、ネオ
ペンチル基、ｎ−ヘキシル基、シクロヘキシル基、ｎ−
オクチル基、ｎ−ドデシル基などのアルキル基、置換ま
たは無置換のフェニル基、ベンジル基およびゲルマシク
ロヘキシル基を挙げることができる。フェニル基および
ベンジル基に置換する置換基としては、メチル基、エチ
ル基、ｎ−プロピル基、ｎ−ブチル基、ｔ−ブチル基な
どのアルキル基、メトキシ基、エトキシ基、ｎ−プロポ
キシ基、ｔ−ブトキシ基などのアルコキシ基、ニトロ
基、シアノ基ならびにこれらアルキル基、アルコキシ
基、ニトロ基、シアノ基の一置換、二置換、三置換体な
どが挙げられる。In the above general formulas (I) and (II), the substituents R 1 to R 3 are methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group. ,
t-butyl group, n-pentyl group, i-pentyl group, neopentyl group, n-hexyl group, cyclohexyl group, n-
Examples thereof include an octyl group, an alkyl group such as n-dodecyl group, a substituted or unsubstituted phenyl group, a benzyl group and a germanocyclohexyl group. Examples of the substituent for substituting the phenyl group and the benzyl group include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a t-butyl group, a methoxy group, an ethoxy group, an n-propoxy group, and t. Examples thereof include an alkoxy group such as a butoxy group, a nitro group and a cyano group, and alkyl, alkoxy, nitro and cyano groups which are mono-substituted, di-substituted and tri-substituted.
【０００８】次に本発明の製法で得られる有機ポリゲル
マンの具体例を式（II）の繰り返し単位との関連で次表
１〜５に示す。 （以下余白）Next, specific examples of the organic polygermane obtained by the production method of the present invention are shown in the following Tables 1 to 5 in relation to the repeating unit of the formula (II). (Below margin)
【表１】 [Table 1]
【表２】 [Table 2]
【表３】 [Table 3]
【表４】 [Table 4]
【表５】 [Table 5]
【０００９】[0009]
【実施例】以下、本発明を実施例により説明するが、本
発明はこれら実施例に限定されるものではない。また、
以下の実施例の反応は、すべて窒素気流下で行った。 実施例１ ジメチルポリゲルマン（ポリマーＮｏ．１）
の製法 ２００ｍｌの丸底フラスコに７０ｍｌのテトラヒドロフ
ランに溶解したビス（ジメチルフェニル）ジゲルモキサ
ン３．７５ｇ（０．０１ｍｏｌ）を入れ、フラスコ内を
窒素置換する。これに室温で窒素ガスを吹き込みなが
ら、低圧水銀灯を６時間照射した。その後、反応生成物
をトルエンで抽出し、無水硫酸マグネシウムで乾燥し
た。トルエンを除去後、真空乾燥を行い、粘性のある液
体のジメチルポリゲルマンを１．２０ｇ得た。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Also,
The reactions in the following examples were all carried out under a nitrogen stream. Example 1 Dimethyl polygermane (Polymer No. 1)
3. Manufacturing method of 3.75 g (0.01 mol) of bis (dimethylphenyl) digermoxane dissolved in 70 ml of tetrahydrofuran was placed in a 200 ml round bottom flask, and the inside of the flask was replaced with nitrogen. This was irradiated with a low pressure mercury lamp for 6 hours while blowing nitrogen gas at room temperature. Then, the reaction product was extracted with toluene and dried over anhydrous magnesium sulfate. After removing toluene, vacuum drying was performed to obtain 1.20 g of viscous liquid dimethylpolygermane.
【００１０】実施例２ フェニルメチルポリゲルマン
（ポリマーＮｏ．１５）の製法 ２００ｍｌの丸底フラスコに８０ｍｌのテトラヒドロフ
ランに溶解したビス（ジフェニルメチル）ジゲルモキサ
ン５．００ｇ（０．０１ｍｏｌ）を入れ、フラスコ内を
窒素置換する。これに室温で窒素ガスを吹き込みなが
ら、低圧水銀灯を１０時間照射した。その後、反応生成
物をトルエンで抽出し、無水硫酸マグネシウムで乾燥し
た。トルエンを除去後、真空乾燥を行い、得られた生成
物を１０ｍｌのトルエンに溶解し、これを１０００ｍｌ
のメタノールに注いで結晶を析出させた。吸引濾過後、
真空乾燥を行って白色結晶のフェニルメチルポリゲルマ
ンを０．７４ｇ得た。Example 2 Method for Producing Phenylmethyl Polygermane (Polymer No. 15) A 200 ml round bottom flask was charged with 5.00 g (0.01 mol) of bis (diphenylmethyl) digermoxane dissolved in 80 ml of tetrahydrofuran. Replace with nitrogen. This was irradiated with a low pressure mercury lamp for 10 hours while blowing nitrogen gas at room temperature. Then, the reaction product was extracted with toluene and dried over anhydrous magnesium sulfate. After removing toluene, vacuum drying is performed, the obtained product is dissolved in 10 ml of toluene, and this is dissolved in 1000 ml.
Was poured into methanol to precipitate crystals. After suction filtration,
Vacuum drying was performed to obtain 0.74 g of white crystalline phenylmethylpolygermane.
【００１１】実施例３ ジフェニルポリゲルマン（ポリ
マーＮｏ．７）の製法 ２００ｍｌの丸底フラスコに８０ｍｌのテトラヒドロフ
ランに溶解したヘキサフェニルジゲルモキサン６．２３
ｇ（０．０１ｍｏｌ）を入れ、フラスコ内を窒素置換す
る。これに室温で窒素ガスを吹き込みながら、低圧水銀
灯を４時間照射した。その後、反応生成物をトルエンで
抽出し、無水硫酸マグネシウムで乾燥した。トルエンを
除去後、真空乾燥を行い、粘性のある液体のジフェニル
ポリゲルマンを０．９６ｇ得た。Example 3 Preparation of Diphenyl Polygermane (Polymer No. 7) Hexaphenyl digermoxane 6.23 dissolved in 80 ml of tetrahydrofuran in a 200 ml round bottom flask.
g (0.01 mol) was added, and the inside of the flask was replaced with nitrogen. This was irradiated with a low pressure mercury lamp for 4 hours while blowing nitrogen gas at room temperature. Then, the reaction product was extracted with toluene and dried over anhydrous magnesium sulfate. After removing toluene, vacuum drying was performed to obtain 0.96 g of viscous liquid diphenylpolygermane.
【００１２】[0012]
【効果】本発明は、出発原料として従来法の有機ゲルマ
ニウム化合物とは異なったジゲルモキサンを選択使用し
た有機ポリゲルマンの新しい製法を開発したものであ
る。本発明の方法により、分子量が５０００前後でその
分子量分布が小さい有機ポリゲルマンを比較的簡単に合
成することができた。また、本発明の方法は従来法より
高収率で有機ポリゲルマンを得ることができた。[Effect] The present invention has developed a new method for producing an organic polygermane by selectively using digermoxane different from the conventional organic germanium compound as a starting material. By the method of the present invention, it was possible to relatively easily synthesize an organic polygermane having a molecular weight of about 5000 and a small molecular weight distribution. In addition, the method of the present invention was able to obtain organic polygermane in a higher yield than the conventional method.
【図１】本発明実施例２のポリマーであるフェニルメチ
ルポリゲルマンのＧＰＣチャート図である。FIG. 1 is a GPC chart of phenylmethylpolygermane, which is a polymer of Example 2 of the present invention.
【図２】本発明実施例２のポリマーであるフェニルメチ
ルポリゲルマンのトルエン溶液での紫外・可視吸収スペ
クトル図である。FIG. 2 is an ultraviolet / visible absorption spectrum diagram of a toluene solution of phenylmethylpolygermane, which is a polymer of Example 2 of the present invention.
【図３】本発明実施例２のポリマーであるフェニルメチ
ルポリゲルマンの反射法で測定した赤外線吸収スペクト
ル図である。FIG. 3 is an infrared absorption spectrum diagram of phenylmethylpolygermane, which is a polymer of Example 2 of the present invention, measured by a reflection method.
Claims (2)
いてもよく、水素原子、炭素数１〜２０のアルキル基、
置換または無置換芳香族基、および置換または無置換脂
環族基よりなる群から選ばれるものである。但し、アル
キル基は互いに結合しＧｅ原子と一緒にＧｅ含有環を形
成することもできる。また、Ｒ3は芳香族置換基を表わ
す。）で示されるジゲルモキサンに光照射させることを
特徴とする、 次式（II） 【化２】 （式中、Ｒ1およびＲ2は、前記に同じ。）で示される繰
り返し単位よりなる有機ポリゲルマンの製法。1. The following formula (I): (In the formula, R1And R2Are the same or different from each other
May be a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
Substituted or unsubstituted aromatic group, and substituted or unsubstituted fat
It is selected from the group consisting of cyclic groups. However,
Kill groups are linked together to form a Ge-containing ring with a Ge atom.
It can also be done. Also, R3Represents an aromatic substituent
You ) Digermoxane
Characterized by the following formula (II) (In the formula, R1And R2Is the same as above. )
A method of manufacturing organic polygermane that consists of repeating units.
する請求項１記載の有機ポリゲルマンの製法。2. The method for producing an organic polygermane according to claim 1, which is carried out in the presence of an inert gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03350997A JP3083613B2 (en) | 1991-12-11 | 1991-12-11 | Manufacturing method of organic polygermane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03350997A JP3083613B2 (en) | 1991-12-11 | 1991-12-11 | Manufacturing method of organic polygermane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05163354A true JPH05163354A (en) | 1993-06-29 |
| JP3083613B2 JP3083613B2 (en) | 2000-09-04 |
Family
ID=18414336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03350997A Expired - Fee Related JP3083613B2 (en) | 1991-12-11 | 1991-12-11 | Manufacturing method of organic polygermane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3083613B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021515822A (en) * | 2018-09-20 | 2021-06-24 | エルジー・ケム・リミテッド | Method for producing high-refractive composition, high-refractive film and high-refractive film |
-
1991
- 1991-12-11 JP JP03350997A patent/JP3083613B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021515822A (en) * | 2018-09-20 | 2021-06-24 | エルジー・ケム・リミテッド | Method for producing high-refractive composition, high-refractive film and high-refractive film |
| US11866584B2 (en) | 2018-09-20 | 2024-01-09 | Lg Chem, Ltd. | High-refractive-index composition, high-refractive-index film, and method for manufacturing high-refractive-index film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3083613B2 (en) | 2000-09-04 |
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