JPH05163355A - Preparation of organopolygermane - Google Patents
Preparation of organopolygermaneInfo
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- JPH05163355A JPH05163355A JP3350998A JP35099891A JPH05163355A JP H05163355 A JPH05163355 A JP H05163355A JP 3350998 A JP3350998 A JP 3350998A JP 35099891 A JP35099891 A JP 35099891A JP H05163355 A JPH05163355 A JP H05163355A
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- polygermane
- substituted
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- organic
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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４】 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(IV）
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（ｂｉｍｏｄａ
ｌ）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 4] 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 (IV)
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 early stage of the reaction, and various germanium intermediates (eg, germanyl radical, gel It is believed that the organic polygermane is produced via mil anion, germylene, germylene anion, gelmen, etc.). The molecular weight distribution of the organic polygermane produced in this manner is bimodal.
l) 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 since it shows a similar distribution in the production of organic polysilane,
It is considered to be a peculiar phenomenon observed in polycondensation using alkali metals. 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、短時間、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] An object of the present invention is to provide a method for producing an organic polygermane having a single peak molecular weight distribution in a short time in a high yield.
【０００４】[0004]
【構成】本発明は、次式（Ｉ）The present invention has the following formula (I)
【化５】 （式中、Ｒ1、Ｒ2およびｎは前記に同じ）で示される環
状ポリゲルマンと次式（II）[Chemical 5] (Wherein R 1 , R 2 and n are the same as described above) and the following formula (II)
【化６】 ＲＭ （II) （式中、ＲおよびＭは前記に同じ）で示される有機金属
化合物とを反応させることを特徴とする次式（III）Embedded image The following formula (III) characterized by reacting with an organometallic compound represented by RM (II) (wherein R and M are the same as above)
【化７】 （式中、Ｒ1およびＲ2とｍは前記に同じ）で示される有
機ポリゲルマンの製法に関する。[Chemical 7] (In the formula, R 1 and R 2 and m are the same as above), and relates to a method for producing an organic polygermane.
【０００５】本発明の製法において、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、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防ぐために不活性ガス下でおこな
うのが好ましい。In the production method of the present invention, the organic solvent used is an ether type such as diethyl ether or tetrahydrofuran, a hydrocarbon type such as pentane, hexane or cyclohexane, or an aromatic hydrocarbon type such as benzene or toluene. it can. When carrying out the reaction, it is preferable to dry these organic solvents in advance before use. Further, the reaction temperature is from -80 ° C to 120 ° C.
Can be performed in the range of. In either reaction, it is preferable to carry out under an inert gas in order to prevent reaction with oxygen in the air.
【０００６】本発明の製法は、例えば、一般式（Ｉ）で
示される環状ポリゲルマンと一般式（II）の有機金属化
合物とを有機溶媒中で反応することで製造される。該反
応は次式（IV）で示されるものである。The production method of the present invention is produced, for example, by reacting a cyclic polygermane represented by the general formula (I) with an organometallic compound represented by the general formula (II) in an organic solvent. The reaction is represented by the following formula (IV).
【化８】 [Chemical 8]
【０００７】本発明の前記一般式（Ｉ）および（III）
中、置換基Ｒ1およびＲ2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。また、本発明に使用される
一般式（II）で示される有機金属化合物中、置換基Ｒと
しては、メチル基、エチル基、ｎ−ブチル基、ｔ−ブチ
ル基などのアルキル基、置換または無置換のフェニル基
を挙げることができる。フェニ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のア
ルキル基、アルコキシ基、ニトロ基、シアノ基を挙げる
ことができる。さらにハロゲン原子としてはクロル、ブ
ロム、ヨードなどを挙げることができる。The above general formulas (I) and (III) of the present invention
Among them, as the substituents R 1 and R 2 , a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
alkyl group such as s-butyl group, t-butyl group, n-pentyl group, i-pentyl group, neopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-dodecyl group, substituted or unsubstituted Mention may be made of phenyl, benzyl and germanocyclohexyl groups. Examples of the substituent that substitutes the phenyl group and the benzyl group include
Methyl group, ethyl group, n-propyl group, n-butyl group,
Alkyl group such as t-butyl group, methoxy group, ethoxy group, n-propoxy group, alkoxy group such as t-butoxy group, nitro group, cyano group and these alkyl groups,
Alkoxy group, nitro group, cyano group mono-substituted, di-substituted,
Examples include tri-substituted compounds. In addition, in the organometallic compound represented by the general formula (II) used in the present invention, the substituent R is an alkyl group such as a methyl group, an ethyl group, an n-butyl group or a t-butyl group, or a substituted or non-substituted group. A substituted phenyl group can be mentioned. Examples of the substituent that substitutes the phenyl 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,
Examples thereof include an ethoxy group, an n-propoxy group, an alkoxy group such as a t-butoxy group, a nitro group and a cyano group, and an alkyl group, an alkoxy group, a nitro group and a cyano group thereof. Further, examples of the halogen atom include chlorine, bromine, iodine and the like.
【０００８】以上のような一般式（Ｉ）の還状ポリゲル
マンおよび（III）の有機ポリゲルマンの具体例を下記
一般式との関連で表１〜１２に示す。本発明の製造方法
で、出発原料として使用する環状ポリゲルマンを表１〜
７に、また本発明の製造方法で得られる有機ポリゲルマ
ンの具体例を繰り返し単位で、表８〜１２にそれぞれ示
す。Specific examples of the reduced polygermane of the general formula (I) and the organic polygermane of the formula (III) are shown in Tables 1 to 12 in relation to the following general formula. The cyclic polygermane used as a starting material in the production method of the present invention is shown in Table 1
7, and specific examples of the organic polygermane obtained by the production method of the present invention are shown as repeating units in Tables 8 to 12, respectively.
【０００９】[0009]
【表１】 [Table 1]
【表２】 [Table 2]
【表３】 [Table 3]
【表４】 [Table 4]
【表５】 [Table 5]
【表６】 [Table 6]
【表７】 [Table 7]
【００１０】[0010]
【表８】 [Table 8]
【表９】 [Table 9]
【表１０】 [Table 10]
【表１１】 [Table 11]
【表１２】 [Table 12]
【００１１】[0011]
【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）
の製造 ２００ｍｌの三つ口フラスコにドデカメチルシクロヘキ
サゲルマン６．１６ｇ（０．０１ｍｏｌ）を１００ｍｌ
のテトラヒドロフランに溶解し、室温でこれに２規定の
ｎ−ブチルリチウムヘキサン溶液５．５ｍｌを滴下し
た。その後、室温で２０時間撹拌をした後、未反応のｎ
−ブチルリチウムを水で分解して、トルエンで抽出し
た。トルエン溶液は無水硫酸マグネシウムで乾燥した。
溶媒を除去後、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１．３４ｇ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)
Preparation of 6.16 g (0.01 mol) of dodecamethylcyclohexagermane in a 200 ml three-necked flask.
Was dissolved in tetrahydrofuran and was added dropwise with 5.5 ml of a 2N n-butyllithium hexane solution at room temperature. Then, after stirring at room temperature for 20 hours, unreacted n
-Butyllithium was decomposed with water and extracted with toluene. The toluene solution was dried over anhydrous magnesium sulfate.
After removing the solvent, vacuum drying was performed to obtain 1.34 g of viscous liquid dimethylpolygermane.
【００１２】実施例２ ジｎ−ブチルポリゲルマン（ポ
リマーＮｏ．３）の製造 ２００ｍｌの三つ口フラスコにオクタｎ−ブチルシクロ
テトラゲルマン７．４７ｇ（０．０１ｍｏｌ）を７０ｍ
ｌのジエチルエーテルに溶解し、室温でこれに２規定の
ｎ−ブチルリチウムヘキサン溶液５．５ｍｌを滴下し
た。その後、室温で６時間撹拌をした後、未反応のｎ−
ブチルリチウムを水で分解して、トルエンで抽出した。
トルエン溶液は無水硫酸マグネシウムで乾燥した。溶媒
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
って白色結晶のジｎ−ブチルポリゲルマンを１．８６ｇ
得た。Example 2 Preparation of di-n-butyl polygermane (Polymer No. 3) In a 200 ml three-necked flask, 7.47 g (0.01 mol) of octa-n-butylcyclotetragermane was added to 70 m.
It was dissolved in 1 l of diethyl ether, and 5.5 ml of a 2N n-butyllithium hexane solution was added dropwise thereto at room temperature. Then, after stirring at room temperature for 6 hours, unreacted n-
Butyllithium was decomposed with water and extracted with toluene.
The toluene solution was dried over anhydrous magnesium sulfate. After removing the solvent, vacuum drying was performed to obtain 10 ml of the obtained product.
Was dissolved in toluene and poured into 1000 ml of methanol to precipitate crystals. After suction filtration, vacuum drying was performed to obtain 1.86 g of white crystalline di-n-butyl polygermane.
Obtained.
【００１３】実施例３ ジｎ−ヘキシルポリゲルマン
（ポリマーＮｏ．５）の製造 ２００ｍｌの三つ口フラスコにオクタｎ−ヘキシルシク
ロテトラゲルマン９．７０ｇ（０．０１ｍｏｌ）を８０
ｍｌのテトラヒドロフランに溶解し、室温でこれに２規
定のｎ−ブチルリチウムヘキサン溶液５．５ｍｌを滴下
した。その後、室温で１０時間撹拌をした後、未反応の
ｎ−ブチルリチウムを水で分解して、トルエンで抽出し
た。トルエン溶液は無水硫酸マグネシウムで乾燥した。
溶媒を除去後、真空乾燥を行い、白色結晶のジｎ−ヘキ
シルポリゲルマンを２．１０ｇ得た。Example 3 Preparation of di-n-hexyl polygermane (Polymer No. 5) Into a 200 ml three-necked flask, octan-n-hexyl cyclotetragermane 9.70 g (0.01 mol) 80 was added.
It was dissolved in ml of tetrahydrofuran and 5.5 ml of a 2N n-butyllithium hexane solution was added dropwise thereto at room temperature. Then, after stirring at room temperature for 10 hours, unreacted n-butyllithium was decomposed with water and extracted with toluene. The toluene solution was dried over anhydrous magnesium sulfate.
After removing the solvent, vacuum drying was performed to obtain 2.10 g of white crystalline di-n-hexyl polygermane.
【００１４】[0014]
【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環状ポリゲルマンを選択使用
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、分子量分布の小さい有機ポリ
ゲルマンを得ることができた。また、本発明の方法は従
来法より短時間、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 using a cyclic polygermane different from the conventional organic germanium compound as a starting material. By the method of the present invention, an organic polygermane having a small molecular weight distribution could be obtained. In addition, the method of the present invention was able to obtain organic polygermane in a high yield in a shorter time than the conventional method.
【図１】本発明実施例２のポリマーであるジｎ−ブチル
ポリゲルマンのＧＰＣチャート図である。FIG. 1 is a GPC chart of di-n-butyl polygermane, which is a polymer of Example 2 of the present invention.
【図２】本発明実施例２のポリマーであるジｎ−ブチル
ポリゲルマンのトルエン溶液での紫外・可視スペクトル
図である。FIG. 2 is an ultraviolet / visible spectrum diagram of a toluene solution of di-n-butyl polygermane, which is a polymer of Example 2 of the present invention.
【図３】本発明実施例２のポリマーであるジｎ−ブチル
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 di-n-butyl polygermane, which is a polymer of Example 2 of the present invention, measured by a reflection method.
【図４】本発明実施例３のポリマーであるジｎ−ヘキシ
ルポリゲルマンのトルエン溶液での紫外・可視スペクト
ル図である。FIG. 4 is an ultraviolet / visible spectrum diagram of a toluene solution of di-n-hexyl polygermane, which is a polymer of Example 3 of the present invention.
【図５】本発明実施例３のポリマーであるジｎ−ヘキシ
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. 5 is an infrared absorption spectrum diagram of di-hexylpolygermane, which is a polymer of Example 3 of the present invention, measured by a reflection method.
Claims (2)
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。ｎは３〜８の整数である。）で示される
環状ポリゲルマンと次式（II） 【化２】 ＲＭ （II) （式中、ＭはＬｉまたはＭｇＸ、Ｘはハロゲン原子、Ｒ
は炭素数１〜４のアルキル基、あるいは置換または無置
換のフェニル基を表わす。）で示される有機金属化合物
とを反応させることを特徴とする次式（III） 【化３】 （式中、Ｒ1、Ｒ2は前記に同じ。ｍは１０〜１００００
の整数を表わす。）で示される有機ポリゲルマンの製
法。1. The following formula (I): (In the formula, R 1 and R 2 may be the same or different from each other, and are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted alicyclic group. The alkyl group may be bonded to each other to form a Ge-containing ring together with a Ge atom, and n is an integer of 3 to 8). RM (II) (wherein M is Li or MgX, X is a halogen atom, R is
Represents an alkyl group having 1 to 4 carbon atoms or a substituted or unsubstituted phenyl group. ) Is reacted with an organometallic compound represented by the following formula (III): (In the formula, R 1 and R 2 are the same as above. M is 10 to 10,000.
Represents the integer. ) The manufacturing method of the organic polygermane shown by.
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 |
|---|---|---|---|
| JP03350998A JP3083614B2 (en) | 1991-12-11 | 1991-12-11 | Manufacturing method of organic polygermane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03350998A JP3083614B2 (en) | 1991-12-11 | 1991-12-11 | Manufacturing method of organic polygermane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05163355A true JPH05163355A (en) | 1993-06-29 |
| JP3083614B2 JP3083614B2 (en) | 2000-09-04 |
Family
ID=18414342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03350998A Expired - Fee Related JP3083614B2 (en) | 1991-12-11 | 1991-12-11 | Manufacturing method of organic polygermane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3083614B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1943669A2 (en) * | 2005-10-05 | 2008-07-16 | Nanogram Corporation | Linear and cross-linked high molecular weight polysilanes, polygermanes, and copolymers thereof, compositions containing the same, and methods of making and using such compounds and compositions |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0563616U (en) * | 1992-01-30 | 1993-08-24 | アイワ株式会社 | air purifier |
-
1991
- 1991-12-11 JP JP03350998A patent/JP3083614B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1943669A2 (en) * | 2005-10-05 | 2008-07-16 | Nanogram Corporation | Linear and cross-linked high molecular weight polysilanes, polygermanes, and copolymers thereof, compositions containing the same, and methods of making and using such compounds and compositions |
| US7943721B2 (en) | 2005-10-05 | 2011-05-17 | Kovio, Inc. | Linear and cross-linked high molecular weight polysilanes, polygermanes, and copolymers thereof, compositions containing the same, and methods of making and using such compounds and compositions |
| EP1943669A4 (en) * | 2005-10-05 | 2012-06-13 | Kovio Inc | POLYSILANES, POLYGERMANES OF LINEAR AND RETICULATED MOLECULAR WEIGHT AND COPOLYMERS THEREOF, COMPOSITIONS CONTAINING THE SAME, AND METHODS OF MAKING AND USING SUCH COMPOUNDS AND COMPOSITIONS |
| US8378050B2 (en) | 2005-10-05 | 2013-02-19 | Kovio, Inc. | Linear and cross-linked high molecular weight polysilanes, polygermanes, and copolymers thereof, compositions containing the same, and methods of making and using such compounds and compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3083614B2 (en) | 2000-09-04 |
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