JP2707688B2 - Polysilane carboxylic acid compound - Google Patents
Polysilane carboxylic acid compoundInfo
- Publication number
- JP2707688B2 JP2707688B2 JP5576889A JP5576889A JP2707688B2 JP 2707688 B2 JP2707688 B2 JP 2707688B2 JP 5576889 A JP5576889 A JP 5576889A JP 5576889 A JP5576889 A JP 5576889A JP 2707688 B2 JP2707688 B2 JP 2707688B2
- Authority
- JP
- Japan
- Prior art keywords
- polysilane
- disilabicyclo
- octa
- diene
- carboxylic acid
- 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.)
- Expired - Lifetime
Links
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は情報電子材料やLB膜材料、プレセラミックス
等の各種機能材料として有用な新規なポリシランポリマ
ーに関するものである。The present invention relates to a novel polysilane polymer useful as various functional materials such as information electronic materials, LB film materials, and preceramics.
従来ポリシランポリマーは種々のものが合成されてき
た。例えば、ポリシラン鎖総てにケイ素原子を置換した
ポリマー（特願昭61−184533号）やポリシラン鎖に異な
ったアルキル基を交互に置換したポリマー（特願昭63−
057087号）等が最近合成されている。Conventionally, various polysilane polymers have been synthesized. For example, a polymer in which all of the polysilane chains are substituted with silicon atoms (Japanese Patent Application No. 61-184533) or a polymer in which the polysilane chains are alternately substituted with different alkyl groups (Japanese Patent Application No. Sho 63-184533).
No. 057087) has recently been synthesized.
しかしながら、ポリシラン鎖の末端にカルボキシル基
を有する化合物は今まで合成されていない。However, a compound having a carboxyl group at the terminal of a polysilane chain has not been synthesized so far.
〔課題を解決するための手段〕 本発明は下記一般式（Ｉ） （式中、R1〜R4は低級アルキル基又はフェニル基を表
し、R1〜R4は同一であっても異なってもよく、R5は低級
アルキル基を表し、ｎは１以上の整数を表す。） で示されるポリシランカルボン酸化合物をその要旨と
するものである。[Means for Solving the Problems] The present invention provides the following general formula (I) (Wherein, R 1 to R 4 represent a lower alkyl group or a phenyl group, R 1 to R 4 may be the same or different, R 5 represents a lower alkyl group, and n is an integer of 1 or more. The gist is a polysilane carboxylic acid compound represented by the following formula.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のポリシランカルボン酸は、上記の一般式
（Ｉ）で表わされる新規な化合物である。ここでR1〜R4
は低級アルキル基又はフェニル基を表し、R5は低級アル
キル基を表し、ｎは１以上の整数を表わすが、好ましく
は、R1〜R4はC1〜C5のアルキル基であって、これらのア
ルキル基は同一又は異っていてもよい。またR5はC1〜C5
のアルキル基を挙げることができ、そしてｎは1000000
以下のものを挙げることができる。The polysilanecarboxylic acid of the present invention is a novel compound represented by the above general formula (I). Where R 1 to R 4
Represents a lower alkyl group or a phenyl group, R 5 represents a lower alkyl group, n represents an integer of 1 or more, preferably, R 1 to R 4 are a C 1 to C 5 alkyl group, These alkyl groups may be the same or different. R 5 is C 1 to C 5
And n is 1,000,000
The following can be mentioned.
本発明において用いるシリレンは、不安定中間体とし
て種々の方法によって合成されるが、好ましくは、下記
一般式（II） （式中、R1〜R4は低級アルキル基又はフェニル基を表
し、R1〜R4は同一であってもことなっていてもよい。Y1
は水素原子又はフェニル基を表す。Y2、Y3、Y4及びY5は
水素原子を表すか、Y2とY3、又はY4とY5が一緒になって で表される芳香環を同時もしくは単独に形成することを
表す。） で示されるジシランのビフェニル、ナフタレンおよびア
ンスラセンの架橋体から発生出来る。The silylene used in the present invention is synthesized as an unstable intermediate by various methods, and is preferably a compound represented by the following general formula (II): (Wherein, R 1 to R 4 represent a lower alkyl group or a phenyl group, and R 1 to R 4 may be the same or different. Y 1
Represents a hydrogen atom or a phenyl group. Y 2 , Y 3 , Y 4 and Y 5 represent a hydrogen atom, or Y 2 and Y 3 , or Y 4 and Y 5 together Represents that the aromatic ring represented by is formed simultaneously or independently. ) Can be generated from a crosslinked product of diphenyl, naphthalene and anthracene of disilane.
ビフェニル体としては、例えば、１−フェニル−7,7,
8,8−テトラメチル−7,8−ジシラビシクロ〔2.2.2〕オ
クタ−2,5−ジエン、１−フェニル−7,7,8−トリメチル
−８−エチル−7,8−ジシラビシクロ〔2.2.2〕オクタ−
2,5−ジエン、１−フェニル−7,7,8−トリメチル−８−
プロピル−7,8−ジシラビシクロ〔2.2.2〕オクタ−2,5
−ジエン、１−フェニル−7,7,8−トリメチル−８−ブ
チル−7,8−ジシラビシクロ〔2.2.2〕オクタ−2,5−ジ
エン、１−フェニル−7,7,8−トリメチル−８−フェニ
ル−7,8−ジシラビシクロ〔2.2.2〕オクタ−2,5−ジエ
ン、１−フェニル−7,8−ジメチル−7,8−ジプロピル−
7,8−ジシラビシクロ〔2.2.2〕オクタ−2,5−ジエン等
が挙げられる。As the biphenyl compound, for example, 1-phenyl-7,7,
8,8-tetramethyl-7,8-disilabicyclo [2.2.2] octa-2,5-diene, 1-phenyl-7,7,8-trimethyl-8-ethyl-7,8-disilabicyclo [2.2.2 Octa
2,5-diene, 1-phenyl-7,7,8-trimethyl-8-
Propyl-7,8-disilabicyclo [2.2.2] octa-2,5
-Diene, 1-phenyl-7,7,8-trimethyl-8-butyl-7,8-disilabicyclo [2.2.2] octa-2,5-diene, 1-phenyl-7,7,8-trimethyl-8 -Phenyl-7,8-disilabicyclo [2.2.2] octa-2,5-diene, 1-phenyl-7,8-dimethyl-7,8-dipropyl-
7,8-disilabicyclo [2.2.2] octa-2,5-diene and the like.
ナフタレン体としては、例えば2,3−ベンゾ−7,7,8,8
−テトラメチル−7,8−ジシラビシクロ〔2.2.2〕オクタ
−2,5−ジエン、2,3−ベンゾ−7,7,8−トリメチル−８
−エチル−7,8−ジシラビシクロ〔2.2.2〕オクタ−2,5
−ジエン、2,3−ベンゾ−7,7,8−トリメチル−８−プロ
ピル−7,8−ジシラビシクロ〔2.2.2〕オクタ−2,5−ジ
エン、2,3−ベンゾ−7,7,8−トリメチル−８−ブチル−
7,8−ジシラビシクロ〔2.2.2〕オクタ−2,5−ジエン、
2,3−ベンゾ−7,7,8−トリメチル−８−フェニル−7,8
−ジシラビシクロ〔2.2.2〕オクタ−2,5−ジエン等が挙
げられる。As naphthalene bodies, for example, 2,3-benzo-7,7,8,8
-Tetramethyl-7,8-disilabicyclo [2.2.2] octa-2,5-diene, 2,3-benzo-7,7,8-trimethyl-8
-Ethyl-7,8-disilabicyclo [2.2.2] octa-2,5
-Diene, 2,3-benzo-7,7,8-trimethyl-8-propyl-7,8-disilabicyclo [2.2.2] octa-2,5-diene, 2,3-benzo-7,7,8 -Trimethyl-8-butyl-
7,8-disilabicyclo [2.2.2] octa-2,5-diene,
2,3-benzo-7,7,8-trimethyl-8-phenyl-7,8
-Disilabicyclo [2.2.2] octa-2,5-diene and the like.
アンスラセン体としては、例えば、2,3:5,6−ジベン
ゾ−7,7,8,8−テトラメチル−7,8−ジシラビシクロ〔2.
2.2〕オクタ−2,5−ジエン、2,3:5,6−ジベンゾ−7,7,8
−トリメチル−８−エチル−7,8−ジシラビシクロ〔2.
2.2〕オクタ−2,5−ジエン、2,3:5,6−ジベンゾ−7,7,8
−トリメチル−８−プロピル−7,8−ジシラビシクロ
〔2.2.2〕オクタ−2,5−ジエン、2,3:5,6−ジベンゾ−
7,7,8−トリメチル−８−ブチル−7,8−ジシラビシクロ
〔2.2.2〕オクタ−2,5−ジエン、2,3:5,6−ジベンゾ−
7,7,8−トリメチル−８−フェニル−7,8−ジシラビシク
ロ〔2.2.2〕オクタ−2,5−ジエン等が挙げられる。As the anthracene compound, for example, 2,3: 5,6-dibenzo-7,7,8,8-tetramethyl-7,8-disilabicyclo [2.
2.2) Octa-2,5-diene, 2,3: 5,6-dibenzo-7,7,8
-Trimethyl-8-ethyl-7,8-disilabicyclo [2.
2.2) Octa-2,5-diene, 2,3: 5,6-dibenzo-7,7,8
-Trimethyl-8-propyl-7,8-disilabicyclo [2.2.2] octa-2,5-diene, 2,3: 5,6-dibenzo-
7,7,8-trimethyl-8-butyl-7,8-disilabicyclo [2.2.2] octa-2,5-diene, 2,3: 5,6-dibenzo-
7,7,8-trimethyl-8-phenyl-7,8-disilabicyclo [2.2.2] octa-2,5-diene and the like.
ポリシランカルボン酸を合成するには、まずシリレン
前駆体である上記一般式（II）で示されるジシラン架橋
体を重合させリビングポリシリレンを調製し、続いてこ
れに二酸化炭素を反応させる。In order to synthesize polysilanecarboxylic acid, first, a crosslinked disilane represented by the above general formula (II), which is a silylene precursor, is polymerized to prepare living polysilylene, and subsequently, carbon dioxide is reacted with this.
重合は一般的なアニオン重合開始剤の存在下に行われ
る。The polymerization is carried out in the presence of a common anionic polymerization initiator.
アニオン重合開始剤及びアニオン重合法としては、例
えば、化学、増刊33号「高分子の合成（II）」113頁、1
968年、化学同人発行に記載されているものを挙げるこ
とができる。Examples of the anionic polymerization initiator and the anionic polymerization method are described in, for example, Kagaku, Supplement No. 33, “Synthesis of Polymer (II)”, page 113, 1
In 968, there can be mentioned those described in Doujin Kagaku.
具体的には、アニオン重合開始剤としては、メチルリ
チウム、ブチルリチウムのようなアルキルリチウム、ク
ミルカリウム、ナトリウムメトキシドのようなアルカリ
金属アルコキシドを挙げることができる。Specifically, examples of the anionic polymerization initiator include alkyl lithium such as methyl lithium and butyl lithium, and alkali metal alkoxide such as cumyl potassium and sodium methoxide.
重合開始剤の使用量としては、架橋体に対して、モル
比で通常0.0001〜10倍好ましくは0.001〜１倍を挙げる
ことができる。The amount of the polymerization initiator to be used is usually 0.0001 to 10 times, preferably 0.001 to 1 time, as a molar ratio, relative to the crosslinked product.
一般に架橋体が固体のため溶媒の使用が必要である。 In general, since the crosslinked product is a solid, it is necessary to use a solvent.
溶媒は極性、無極性いずれでも良いが、好ましくは、
エーテル、THF、ベンゼン、トルエン、キシレンのよう
な非プロトン性溶媒が良い。The solvent may be polar or nonpolar, but preferably,
Aprotic solvents such as ether, THF, benzene, toluene, xylene are preferred.
溶媒の使用量は架橋体1g当たり、通常1ml〜100l、好
ましくは10ml〜１を挙げることができる。The amount of the solvent used is usually 1 ml to 100 l, preferably 10 ml to 1 per g of the crosslinked product.
二酸化炭素としては、炭酸ガス又はドライアイスいず
れでも良い。二酸化炭素は停止剤としても用いられる。As carbon dioxide, either carbon dioxide gas or dry ice may be used. Carbon dioxide is also used as a terminator.
ジシラン架橋体に対する二酸化炭素の量は任意である
が過剰量用いるのが良い。The amount of carbon dioxide with respect to the crosslinked disilane is optional, but is preferably used in excess.
反応温度は任意であるが、通常−150〜120℃で行われ
る。Although the reaction temperature is arbitrary, it is usually carried out at -150 to 120 ° C.
反応は常圧もしくは真空下で行われる。 The reaction is performed under normal pressure or under vacuum.
反応終了後、再沈法又はGPCによる分取等、一般的な
方法によって、目的の重合物を取り出すことができる。After completion of the reaction, the desired polymer can be taken out by a general method such as reprecipitation or fractionation by GPC.
本発明は、特定のシリレンを重合させて得られるリビ
ングポリシリレンに二酸化炭素を反応させることにより
目的のポリシランカルボン酸が得られるものと考えられ
る。In the present invention, it is considered that an objective polysilanecarboxylic acid is obtained by reacting carbon dioxide with living polysilylene obtained by polymerizing a specific silylene.
以下に実施例を挙げて本発明を更に具体的に説明する
が、本発明は以下の実施例によって限定されるものでは
ない。Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
実施例１ １−フェニル−7,8−ジメチル−7,8−ジプロピル−7,
8−ジシラビシクロ〔2.2.2〕オクタ−2,5−ジエン
（１）3.48g（11.2mmol）のTHF溶液60mlを封管中に仕込
み、−78℃に冷却した後、高真空下、ｎ−ブチルリチウ
ム（Ｍ）を0.21mmol含む1mlトルエン溶液を添加し室温
で重合をおこなった。６時間後にドライアイスを溶液の
色が消えるまで加えた。Example 1 1-phenyl-7,8-dimethyl-7,8-dipropyl-7,
60 ml of a THF solution of 3.48 g (11.2 mmol) of 8-disilabicyclo [2.2.2] octa-2,5-diene (1) was charged into a sealed tube, cooled to -78 ° C, and then n-butyl was added under high vacuum. A 1 ml toluene solution containing 0.21 mmol of lithium (M) was added and polymerization was performed at room temperature. After 6 hours, dry ice was added until the color of the solution disappeared.
溶媒留去後、再沈澱法によって白色固体ポリマーを得
た（収率40％）。After evaporating the solvent, a white solid polymer was obtained by a reprecipitation method (yield: 40%).
1H−NMR及びUVスペクトルにより、このポリマーが下
記式であらわされるポリシランカルボン酸であると同定
した。 From 1 H-NMR and UV spectrum, this polymer was identified as polysilane carboxylic acid represented by the following formula.
このポリマーの赤外吸収スペクトルでは、1647cm-1、
1689cm-1にＣ＝Ｏ伸縮振動の吸収が観測された。 In the infrared absorption spectrum of this polymer, 1647 cm −1 ,
At 1689 cm -1 , absorption of C = O stretching vibration was observed.
1H−NMRスペクトル（CDCl3、300MHz） δ;0.23（ｄ）,0.82（ｍ）,0.96（ｍ）,1.38（ｍ） 実施例２〜４ 第１表に示すジシラン架橋体（１）とブチルリチウム
（Ｍ）との量比および反応条件以外は実施例１と同様に
おこなった。 1 H-NMR spectrum (CDCl 3 , 300 MHz) δ; 0.23 (d), 0.82 (m), 0.96 (m), 1.38 (m) Examples 2 to 4 Disilane crosslinked product (1) shown in Table 1 and butyl The same procedures as in Example 1 were carried out except for the amount ratio to lithium (M) and the reaction conditions.
実施例１で得られたポリシランカルボン酸化合物の分
子量分布をゲルパーミエーションクロマトグラフィー
（GPC）により測定し、第１図を得た。 The molecular weight distribution of the polysilane carboxylic acid compound obtained in Example 1 was measured by gel permeation chromatography (GPC), and FIG. 1 was obtained.
本発明化合物は末端にカルボン酸基を結合しているた
め、長鎖カルボン酸の一種とみなすことが出来る。この
ためポリシランの性質を持ったLB膜として応用出来る。Since the compound of the present invention has a carboxylic acid group bonded to the terminal, it can be regarded as a kind of long-chain carboxylic acid. Therefore, it can be applied as an LB film having the properties of polysilane.
あるいは、リジッドディスク等の表面潤滑膜としても
応用出来る。Alternatively, it can be applied as a surface lubricating film for a rigid disk or the like.
本発明の新規なポリシランカルボン酸化合物はLB膜、
プレセラミックス、導電材料、半導体等の材料として有
用な化合物である。The novel polysilanecarboxylic acid compound of the present invention is an LB film,
It is a compound useful as a material for preceramics, conductive materials, semiconductors, and the like.
第１図は、実施例１で得られたポリシラン酸化合物のGP
Cによる分子量分布曲線を示す図である。FIG. 1 shows the GP of the polysilane compound obtained in Example 1.
FIG. 4 is a diagram showing a molecular weight distribution curve by C.
Claims (1)
し、R1〜R4は同一であっても異なってもよく、R5は低級
アルキル基を表し、ｎは１以上の整数を表す。） で示されるポリシランカルボン酸化合物。1. A compound represented by the following general formula (I) (Wherein, R 1 to R 4 represent a lower alkyl group or a phenyl group, R 1 to R 4 may be the same or different, R 5 represents a lower alkyl group, and n is an integer of 1 or more. The polysilane carboxylic acid compound represented by these.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5576889A JP2707688B2 (en) | 1989-03-08 | 1989-03-08 | Polysilane carboxylic acid compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5576889A JP2707688B2 (en) | 1989-03-08 | 1989-03-08 | Polysilane carboxylic acid compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02235934A JPH02235934A (en) | 1990-09-18 |
| JP2707688B2 true JP2707688B2 (en) | 1998-02-04 |
Family
ID=13008045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5576889A Expired - Lifetime JP2707688B2 (en) | 1989-03-08 | 1989-03-08 | Polysilane carboxylic acid compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2707688B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1943669A4 (en) | 2005-10-05 | 2012-06-13 | 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 |
-
1989
- 1989-03-08 JP JP5576889A patent/JP2707688B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02235934A (en) | 1990-09-18 |
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