JPH07277760A - Transparent bulk silica material containing organic group and its production - Google Patents
Transparent bulk silica material containing organic group and its productionInfo
- Publication number
- JPH07277760A JPH07277760A JP8749794A JP8749794A JPH07277760A JP H07277760 A JPH07277760 A JP H07277760A JP 8749794 A JP8749794 A JP 8749794A JP 8749794 A JP8749794 A JP 8749794A JP H07277760 A JPH07277760 A JP H07277760A
- Authority
- JP
- Japan
- Prior art keywords
- organotrialkoxysilane
- water
- organic group
- molar ratio
- distilled water
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/12—Other methods of shaping glass by liquid-phase reaction processes
Abstract
Description
【０００１】産業上の利用分野 本発明は有機基を含有した透明シリカバルク体及びその
製造方法に関し、とりわけ、光機能を有する有機物のホ
スト材料として有望な有機基含有透明シリカバルク体及
びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic group-containing transparent silica bulk body and a method for producing the same, and more particularly, an organic group-containing transparent silica bulk body which is promising as a host material for an organic substance having an optical function and a method for producing the same. Regarding
【０００２】従来の技術及び課題 ゾル−ゲル法によるガラス、セラミック等の合成におい
ては、通常、多くのアルコールなどの溶媒を用いるた
め、乾燥の際の体積の減少が大きく、特にバルク体作製
時にはクラックが入るという課題を有している。この課
題を解決する方法が種々提案されているが、得られるゲ
ル体は本質的に多孔質であり、根本的な解決には至って
いない。2. Description of the Related Art In the synthesis of glass, ceramics and the like by the sol-gel method, a large amount of solvent such as alcohol is usually used, so that the volume is greatly reduced during drying, and cracks are generated especially when a bulk body is manufactured. Has the problem of entering. Various methods for solving this problem have been proposed, but the obtained gel body is essentially porous, and a fundamental solution has not been reached yet.
【０００３】また、従来から光機能を有する有機物質を
ドープしたシリカゲル体等の合成がゾル−ゲル法によっ
て行われている「Ｔａｎｉ ｅｔ ａｌ，Ｊ．Ａｐｐ
ｌ．Ｐｈｙｓ．５８（１９８５）３５５９；Ａｖｎｉｒ
ｅｔ ａｌ，Ｊ．Ｐｈｙ．Ｃｈｅｍ．８８（１９８
４）５９５６．等」がマトリックスの骨格構造が三次元
的に発達しているものが多く、分子量の大きい有機物質
をも高濃度でドープするには骨格中の隙間の大きさは十
分とは言えなかった。Further, "Tani et al, J. App," which has been conventionally used to synthesize a silica gel body doped with an organic substance having an optical function, by a sol-gel method.
l. Phys. 58 (1985) 3559; Avnir.
et al, J .; Phy. Chem. 88 (198
4) 5956. In many cases, the skeleton structure of the matrix is three-dimensionally developed, and the size of the gap in the skeleton was not sufficient to dope high-molecular-weight organic substances at high concentrations.
【０００４】一方、ゾル−ゲル法においては、急速な加
水分解反応や溶解度等に起因したゲル化前の沈殿生成や
分相現象が起こりうることが知られている。分相現象
は、メチル基含有シリカコーティング膜の作製の研究に
おいても報告されている。沈殿生成や分相はゲル体の均
一性に大きく影響し、光学材料の特性を損ねるので、マ
トリックスの作製時これらの現象をいかに抑えるかが課
題となっていた。On the other hand, in the sol-gel method, it is known that a rapid hydrolysis reaction, a precipitation and the like before gelation or a phase separation phenomenon due to solubility can occur. The phase separation phenomenon has also been reported in a study on the production of a silica coating film containing a methyl group. Precipitation and phase separation greatly affect the homogeneity of the gel body and impair the properties of the optical material. Therefore, how to suppress these phenomena during the preparation of the matrix has been an issue.
【０００５】従って、本発明はオルガノトリアルコキシ
シランを原料とし、ゾル−ゲル法により、ゲルの乾燥時
の体積減少を極めて小さく、すなわちクラックの発生が
なく、分子量の大きい有機物質をも高濃度でドープする
のに十分な骨格中の隙間の大きさを持ち、かつゲル化前
の沈殿生成や分相のない均一な有機基含有透明シリカバ
ルク体を作製することを目的とする。Therefore, the present invention uses organotrialkoxysilane as a raw material, and by the sol-gel method, the volume reduction of the gel during drying is extremely small, that is, cracks are not generated and an organic substance having a large molecular weight is also highly concentrated. It is an object of the present invention to prepare a transparent bulk silica material having a uniform organic group, which has a sufficient size of a skeleton in the skeleton to be doped, and is free from precipitation before gelation and phase separation.
【０００６】本発明の概要 本発明は、式：ＲＳｉＯ3/2 で示されるネットワーク構
成単位が三次元網目構造を形成するように反復結合して
いるポリシロキサンよりなる有機基含有透明シリカバル
ク体に関する。式中、Ｒは炭素原子によりケイ素原子へ
結合している有機基、典型的にはメチル、エチル、ｎ−
プロピル、イソプロピル、フェニル、ビニル等の炭化水
素基である。SUMMARY OF THE INVENTION The present invention relates to an organic-group-containing transparent silica bulk body composed of polysiloxane in which network constituent units represented by the formula: RSiO 3/2 are repeatedly bonded so as to form a three-dimensional network structure. . In the formula, R is an organic group bonded to a silicon atom by a carbon atom, typically methyl, ethyl, n-
Hydrocarbon groups such as propyl, isopropyl, phenyl and vinyl.
【０００７】この有機基含有透明シリカバルク体は、
式：ＲＳｉ（ＯＲ’）3 （Ｒ’はメチル、エチルなどの
低級アルキル基）のオルガノトリアルコキシシランを出
発原料とし、ゾル−ゲル法によって製造することができ
る。The organic group-containing transparent silica bulk material is
The organotrialkoxysilane of the formula: RSi (OR ′) 3 (R ′ is a lower alkyl group such as methyl or ethyl) can be used as a starting material and can be produced by the sol-gel method.
【０００８】本発明によれば、前記オルガノトリアルコ
キシシランの加水分解および脱水、脱アルコール縮合に
よるシロキサン結合形成の重縮合反応にアルコール系溶
媒を使用しない。そして、第１の方法では、前記オルガ
ノトリアルコキシシランに対し、理論量ないし過剰（モ
ル比で１．５≦Ｈ2 Ｏ／Ｓｉ≦３．０）の水を一時に添
加して反応せしめた後、開放系において反応物を熟成し
てゲル化させる。第２の方法では初回は理論量未満（モ
ル比で１．０≦Ｈ2 Ｏ／Ｓｉ＜１．５）の水と反応さ
せ、最終回までに初回から積算して理論量ないし過剰
（モル比で１．５≦Ｈ2 Ｏ／Ｓｉ≦２．０）となるよう
な追加量の水と反応させ、この間に水の積算量が１．５
≦Ｈ2 Ｏ／Ｓｉとなる以前に任意の段階で、副生したア
ルコールを合計で少なくとも５０％除去した後、開放系
において反応物を熟成してゲル化させる。According to the present invention, an alcohol solvent is not used in the polycondensation reaction for forming a siloxane bond by hydrolysis, dehydration and dealcoholization of the organotrialkoxysilane. Then, in the first method, after a theoretical amount or excess (1.5 ≦ H 2 O / Si ≦ 3.0 in a molar ratio) of water is added to the organotrialkoxysilane at one time and reacted. The reaction product is aged and gelled in an open system. In the second method, the initial reaction is performed with water that is less than the theoretical amount (1.0 ≦ H 2 O / Si <1.5 in molar ratio), and the theoretical amount or excess (molar ratio) is added from the first time until the final time. At a rate of 1.5 ≦ H 2 O / Si ≦ 2.0), and the cumulative amount of water is 1.5
At any stage prior to <H 2 O / Si, at least 50% total by-product alcohol is removed, after which the reaction is aged and gelled in an open system.
【０００９】好ましい実施態様 良く知られているように、オルガノジアルコキシシラン
を加水分解すると対応する２官能のシラノールが生成
し、脱水縮合反応により鎖状または環状のポリシロキサ
ンが生成する。オルガノトリアルコキシシランでは、３
官能のシラノールが生成するので、その脱水縮合反応に
より生成したポリシロキサンは、ネットワーク構成単位
がＲＳｉＯ3/2 （Ｒは前記に同じ。）である三次元網目
構造を取る。 Preferred Embodiment As is well known, when an organodialkoxysilane is hydrolyzed, a corresponding bifunctional silanol is produced, and a chain condensation or a cyclic polysiloxane is produced by a dehydration condensation reaction. 3 for organotrialkoxysilane
Since the functional silanol is produced, the polysiloxane produced by the dehydration condensation reaction has a three-dimensional network structure in which the network constitutional unit is RSiO 3/2 (R is the same as above).
【００１０】このように、ネットワークの構成単位をＲ
ＳｉＯ3/2 とすることによりマトリックスのネットワー
クの骨格中の隙間の大きさが十分大きくなり、分子量の
大きい有機物質の高濃度ドープが可能となる。含有され
る有機基Ｒは、典型的にはメチル基、エチル基、ｎ−プ
ロピル基、イソプロピル基、フェニル基、ビニル基のよ
うな炭化水素基であり、もちろん２種以上の有機基が含
まれていても良い。炭素数がより大きな有機基を導入し
ようとしてもゲル化時間が長くなりすぎる。骨格中の隙
間の大きさを大きくするには、メチル基が最も好ましい
が、ドープする有機物質の種類、量に応じて適宜選択す
ればよい。In this way, the network unit is R
By using SiO 3/2 , the size of the gap in the skeleton of the network of the matrix becomes sufficiently large, and high-concentration doping of an organic substance having a large molecular weight becomes possible. The contained organic group R is typically a hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a phenyl group and a vinyl group, and, of course, contains two or more kinds of organic groups. It may be. Even if an organic group having a higher carbon number is introduced, the gelation time becomes too long. In order to increase the size of the gap in the skeleton, the methyl group is most preferable, but it may be appropriately selected depending on the type and amount of the organic substance to be doped.
【００１１】前記有機基含有透明シリカバルク体の製造
方法において、有機基Ｒとしてメチル基が含まれない場
合には、出発原料にアルコール系溶媒を添加せず、ＲＳ
ｉ（ＯＲ’）3 （Ｒ，Ｒ’は前記に同じ。）に１．５≦
Ｈ2 Ｏ／Ｓｉ≦３．０（モル比）となるように水を添加
し、加水分解・重縮合反応を行う。この際、アルコール
が多量に含まれていると、（ＲＳｉＯ3/2 ）n の結晶が
析出してしまう。水の添加量がＨ2 Ｏ／Ｓｉ＜１．５
（モル比）では、未反応のアルコキシ基が残り、マトリ
ックスの強度が劣化する。逆にＨ2 Ｏ／Ｓｉ＞３．０
（モル比）では分相が起こり、光学的に均質なシリカバ
ルク体が得られない。反応後の熟成は反応により生成し
たアルコールが揮発するように開放系で行う。上記の方
法で反応を進行させることにより結晶化及び／又は沈殿
生成を抑制でき、所望のシリカバルク体を得ることがで
きる。In the method for producing a transparent silica bulk body containing an organic group, when a methyl group is not contained as the organic group R, an alcohol solvent is not added to the starting material and RS is used.
i (OR ′) 3 (R and R ′ are the same as above) 1.5 ≦
Water is added so that H 2 O / Si ≦ 3.0 (molar ratio), and a hydrolysis / polycondensation reaction is performed. At this time, if the alcohol is contained in a large amount, crystals of (RSiO 3/2 ) n will be precipitated. The amount of water added is H 2 O / Si <1.5
At (molar ratio), unreacted alkoxy groups remain and the strength of the matrix deteriorates. Conversely, H 2 O / Si> 3.0
At (molar ratio), phase separation occurs and an optically homogeneous silica bulk body cannot be obtained. The aging after the reaction is performed in an open system so that the alcohol generated by the reaction is volatilized. Crystallization and / or precipitation can be suppressed by advancing the reaction by the above method, and a desired silica bulk material can be obtained.
【００１２】また、前記有機基含有透明シリカバルク体
の製造方法において有機基Ｒとしてメチルが含まれる場
合には出発原料にアルコール系溶媒を添加せず、更に理
論量未満の水との部分加水分解・重縮合反応で生成する
アルコールの少なくとも５０％を系外へ除去することが
必要である。ここで、生成したアルコールの系外への除
去はアルコールの沸点以下の温度で行う。２回目以降の
水の添加の際に均一溶液を得るためには、少量のアルコ
ールが残っていることが好ましいが、多量に含まれてい
ると反応の進行に従って（ＲＳｉＯ3/2 ）n の結晶が析
出する。この方法においては、水の添加は２段階以上に
分けて行う。第１段階の水の添加量は１．０≦Ｈ2 Ｏ／
Ｓｉ＜１．５（モル比）とする。Ｈ2 Ｏ／Ｓｉ＜１．０
では生成したアルコールを系外へ除去する際、未反応の
モノマーも揮散してしまう。逆にＨ2 Ｏ／Ｓｉ≧１．５
では結晶化が起こる。最終的に、水の添加量は第１段階
からの積算で１．５≦Ｈ2 Ｏ／Ｓｉ≦２．０（モル比）
となるように行う。全体の水の量が、Ｈ2 Ｏ／Ｓｉ＜
１．５（モル比）では未反応のアルコキシ基が残り、マ
トリックスの強度が劣化する。逆にＨ2 Ｏ／Ｓｉ＞２．
０では分相が起こり、光学的に均質なシリカバルク体が
得られない。段階的な水の添加に際しては、水の積算量
が１．５≦Ｈ2 Ｏ／Ｓｉとなる以前に、それまで副生し
たアルコールを合計で少なくとも５０％、任意段階で除
去することが必要である。反応後の熟成は反応により生
成したアルコールが揮発するように開放系で行う。上記
の方法で反応を進行させることより、結晶化および／又
は沈殿生成を抑制でき、所望のシリカバルク体を得るこ
とができる。When methyl is contained as the organic group R in the method for producing a transparent silica bulk material containing an organic group, an alcohol solvent is not added to the starting material, and partial hydrolysis with water less than the theoretical amount is carried out. -It is necessary to remove at least 50% of the alcohol produced by the polycondensation reaction from the system. Here, the generated alcohol is removed from the system at a temperature not higher than the boiling point of the alcohol. It is preferable that a small amount of alcohol remains in order to obtain a uniform solution in the second and subsequent additions of water, but if a large amount of alcohol is contained, (RSiO 3/2 ) n crystals are formed as the reaction progresses. Is deposited. In this method, water is added in two or more stages. The amount of water added in the first stage is 1.0 ≦ H 2 O /
Si <1.5 (molar ratio). H 2 O / Si <1.0
Then, when the generated alcohol is removed from the system, unreacted monomers are also volatilized. Conversely, H 2 O / Si ≧ 1.5
Then crystallization occurs. Finally, the added amount of water is 1.5 ≦ H 2 O / Si ≦ 2.0 (molar ratio) in terms of integration from the first step.
To do so. The total amount of water is H 2 O / Si <
At 1.5 (molar ratio), unreacted alkoxy groups remain, and the strength of the matrix deteriorates. Conversely, H 2 O / Si> 2.
At 0, phase separation occurs and an optically homogeneous silica bulk body cannot be obtained. In the stepwise addition of water, it is necessary to remove at least 50% of the by-produced alcohol in total at any stage before the cumulative amount of water becomes 1.5 ≦ H 2 O / Si. is there. The aging after the reaction is performed in an open system so that the alcohol generated by the reaction is volatilized. By proceeding the reaction by the above method, crystallization and / or precipitation formation can be suppressed, and a desired silica bulk material can be obtained.
【００１３】出発原料溶液は前記オルガノトリアルコキ
シシラン、水、触媒を含んでおり、触媒としては硝酸、
塩酸等の無機酸触媒、酢酸等の有機酸触媒、アンモニア
等の塩基触媒が常法に従って使用される。The starting material solution contains the organotrialkoxysilane, water and a catalyst, and the catalyst is nitric acid,
An inorganic acid catalyst such as hydrochloric acid, an organic acid catalyst such as acetic acid, and a base catalyst such as ammonia are used according to a conventional method.
【００１４】尚、加水分解・重縮合反応は室温で行って
も良いが、反応促進のため４０〜８０℃で行うことが好
ましい。The hydrolysis / polycondensation reaction may be carried out at room temperature, but it is preferably carried out at 40 to 80 ° C. to accelerate the reaction.
【００１５】式ＲＳｉ（ＯＲ’）3 のオルガノトリアル
コキシシランの具体例としてはメチルトリメトキシシラ
ン、メチルトリエトキシシラン、メチルトリプロポキシ
シラン、エチルトリメトキシシラン、エチルトリエトキ
シシラン、フェニルトリエトキシシラン、ビニルトリエ
トキシシラン等を用いることができる。Ｒの炭素数が増
加するにつれ、結晶が生成し難くなるが、ネットワーク
の構造にとってはメチル基が最も好ましい。従ってドー
プする有機物質の種類、量に応じて適宜選択される。Specific examples of the organotrialkoxysilane of the formula RSi (OR ') 3 include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, Vinyltriethoxysilane or the like can be used. As the carbon number of R increases, it becomes more difficult to form crystals, but the methyl group is most preferable for the structure of the network. Therefore, it is appropriately selected according to the type and amount of the organic substance to be doped.
【００１６】実施例１ メチルトリエトキシシラン（信越化学工業、ＬＳ−１８
９０、以下ＭＴＥＳ）に、蒸留水とＭＴＥＳのモル比が
１．２５：１になるように蒸留水を添加した。蒸留水の
１０ｗｔ％の水は触媒として０．１Ｎの硝酸を用いた。
最初は２相の状態であるが、内温４０〜５０℃で攪拌を
続けると、加水分解・重縮合反応が進むにつれて均一に
なり、１０分間以内に透明になった。密閉の状態で同温
度に２日間静置した後、反応によって生成したアルコー
ルを理論値の８０％減圧下蒸発させ、更にＭＴＥＳ１モ
ルあたり０．５モルの蒸留水を追加した。密閉の状態で
２時間内温４０〜５０℃で攪拌反応させた後、開放にし
て４０℃の乾燥器中に放置した。得られたゲル体は透明
であり、粉末Ｘ線回折でも、結晶の検出はできなかっ
た。Example 1 Methyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., LS-18)
90, hereinafter MTES), distilled water was added so that the molar ratio of distilled water and MTES was 1.25: 1. As 10 wt% of distilled water, 0.1N nitric acid was used as a catalyst.
Initially, it was in a two-phase state, but when stirring was continued at an internal temperature of 40 to 50 ° C., it became uniform as the hydrolysis / polycondensation reaction proceeded, and became transparent within 10 minutes. After standing at the same temperature for 2 days in a sealed state, the alcohol produced by the reaction was evaporated under reduced pressure of 80% of the theoretical value, and 0.5 mol of distilled water was further added to 1 mol of MTES. After stirring and reacting for 2 hours at an internal temperature of 40 to 50 ° C in a sealed state, the mixture was opened and left in a drier at 40 ° C. The obtained gel body was transparent, and crystals could not be detected by powder X-ray diffraction.
【００１７】実施例２ ＭＴＥＳに、蒸留水とＭＴＥＳのモル比が１．３３：１
になるように蒸留水を添加した。蒸留水の１０ｗｔ％の
水は触媒として０．１Ｎの硝酸を用いた。最初は２相の
状態であるが、内温４０〜５０℃で攪拌を続けると、加
水分解・重縮合反応が進むにつれて均一になり、１０分
間以内に透明になった。密閉の状態で同温度で２日間静
置した後、反応によって生成したアルコールを理論値の
８０％減圧下蒸発させ、更にＭＴＥＳ１モルあたり０．
１７モルの蒸留水を追加した。密閉の状態で内温４０〜
５０℃で２時間反応させた後、開放にして４０℃の乾燥
器中に放置した。得られたゲル体は透明であり、粉末Ｘ
線回折でも、結晶の検出はできなかった。Example 2 MTES has a molar ratio of distilled water to MTES of 1.33: 1.
Distilled water was added so that As 10 wt% of distilled water, 0.1N nitric acid was used as a catalyst. Initially, it was in a two-phase state, but when stirring was continued at an internal temperature of 40 to 50 ° C., it became uniform as the hydrolysis / polycondensation reaction proceeded, and became transparent within 10 minutes. After standing still at the same temperature for 2 days in a sealed state, the alcohol produced by the reaction was evaporated under a reduced pressure of 80% of the theoretical value, and further 0.
Added 17 moles of distilled water. Inner temperature 40 ~ in a sealed state
After reacting at 50 ° C for 2 hours, the mixture was opened and left in a dryer at 40 ° C. The obtained gel body is transparent and powder X
Crystals could not be detected even by line diffraction.
【００１８】実施例３ ＭＴＥＳに、蒸留水とＭＴＥＳのモル比が１．３３：１
になるように蒸留水を添加した。蒸留水の１０ｗｔ％の
水は触媒として０．１Ｎの硝酸を用いた。最初は２相の
状態であるが、内温４０〜５０℃で攪拌を続けると、加
水分解・重縮合反応が進むにつれ均一になり、１０分間
以内に透明になった。得られた溶液を密閉の状態で同温
度で２日間静置した後、反応によって生成したアルコー
ルを理論値の８０％減圧下蒸発させ、更にＭＴＥＳ１モ
ルあたり０．６７モルの蒸留水を追加した。続いて、密
閉の状態で内温４０〜５０℃で２時間反応させた。この
間にゲル化した。更に、開放にして４０℃の乾燥器内に
放置した。得られたゲル体は透明であり、粉末Ｘ線回折
でも、結晶の検出はできなかった。Example 3 MTES has a molar ratio of distilled water to MTES of 1.33: 1.
Distilled water was added so that As 10 wt% of distilled water, 0.1N nitric acid was used as a catalyst. Initially, it was in a two-phase state, but when stirring was continued at an internal temperature of 40 to 50 ° C., it became uniform as the hydrolysis / polycondensation reaction proceeded, and became transparent within 10 minutes. The obtained solution was allowed to stand still at the same temperature for 2 days in a sealed state, the alcohol produced by the reaction was evaporated under reduced pressure of 80% of the theoretical value, and 0.67 mol of distilled water per mol of MTES was further added. Then, it was made to react for 2 hours at an internal temperature of 40 to 50 ° C. in a sealed state. During this time, gelation occurred. Further, it was opened and left in a dryer at 40 ° C. The obtained gel body was transparent, and crystals could not be detected by powder X-ray diffraction.
【００１９】比較例１ ＭＴＥＳに、蒸留水とＭＴＥＳのモル比が１．５：１に
なるように蒸留水を添加した。蒸留水の１０ｗｔ％の水
は触媒として０．１Ｎの硝酸を用いた。最初は２相の状
態であるが、内温４０〜５０℃で攪拌を続けると、加水
分解・重縮合反応が進むにつれて均一になり、１０分間
以内に透明になった。密閉の状態で室温で６ケ月間静置
したところ、ゲルの底部に粒径が数μｍの沈殿が生成し
た。粉末Ｘ線回折で調べたところ、Ｃ8 Ｈ24Ｏ12Ｓｉ8
結晶であることがわかった。ゲル層は白濁しており、結
晶の析出が確認された。Comparative Example 1 Distilled water was added to MTES so that the molar ratio of distilled water and MTES was 1.5: 1. As 10 wt% of distilled water, 0.1N nitric acid was used as a catalyst. Initially, it was in a two-phase state, but when stirring was continued at an internal temperature of 40 to 50 ° C., it became uniform as the hydrolysis / polycondensation reaction proceeded, and became transparent within 10 minutes. When left in a sealed state at room temperature for 6 months, a precipitate having a particle size of several μm was formed at the bottom of the gel. When examined by powder X-ray diffraction, it was found to be C 8 H 24 O 12 Si 8
It was found to be crystalline. The gel layer was cloudy, and the precipitation of crystals was confirmed.
【００２０】比較例２ ＭＴＥＳに、蒸留水とＭＴＥＳのモル比が１．２５：１
になるように蒸留水を添加した。蒸留水の１０ｗｔ％の
水は触媒として０．１Ｎの硝酸を用いた。最初は２相の
状態であるが、内温４０〜５０℃で攪拌を続けると、加
水分解・重縮合反応が進むにつれて均一になり、１０分
間以内に透明になった。得られた溶液を密閉の状態で同
温度で２日間静置した後、反応によって生成したアルコ
ールを理論値の８０％減圧下蒸発させ、更にＭＴＥＳ１
モルあたり１．０モルの蒸留水を追加した。続いて、密
閉の状態で内温４０〜５０℃で２時間反応させた。この
間に、ゲル化した。更に、開放にして４０℃の乾燥器中
に放置したところ、最終的に白濁したゲルを得た。粉末
Ｘ線回折法で調べたところ、結晶の検出はできなかっ
た。Comparative Example 2 MTES has a molar ratio of distilled water and MTES of 1.25: 1.
Distilled water was added so that As 10 wt% of distilled water, 0.1N nitric acid was used as a catalyst. Initially, it was in a two-phase state, but when stirring was continued at an internal temperature of 40 to 50 ° C., it became uniform as the hydrolysis / polycondensation reaction proceeded, and became transparent within 10 minutes. The obtained solution was allowed to stand in the sealed state at the same temperature for 2 days, and then the alcohol produced by the reaction was evaporated under reduced pressure of 80% of the theoretical value, and MTES1 was added.
Added 1.0 mole distilled water per mole. Then, it was made to react for 2 hours at an internal temperature of 40 to 50 ° C. in a sealed state. During this time, gelation occurred. Further, when opened and left in a dryer at 40 ° C., a cloudy gel was finally obtained. When examined by powder X-ray diffractometry, no crystals could be detected.
【００２１】実施例４ メチルトリメトキシシラン（信越化学工業、ＬＳ−５３
０、以下ＭＴＭＳ）に、蒸留水とＭＴＭＳのモル比が
１：１になるように蒸留水を添加した。蒸留水の１０ｗ
ｔ％は触媒として０．１Ｎの硝酸を用いた。最初は２相
の状態であるが、内温４０〜５０℃で攪拌を続けると、
加水分解・重縮合反応が進むにつれて均一になり、１分
間以内に透明になった。密閉の状態で同温度で２日間静
置した後、反応によって生成したアルコールを理論量の
８０％減圧下蒸発させ、更にＭＴＭＳ１モルあたり０．
２５モルの蒸留水を追加した。密閉の状態でさらに３０
分間同温度で反応させた後、再び反応によって生成した
アルコールを理論量の８０％減圧下蒸発させ、更にＭＴ
ＭＳ１モルあたり０．５モルの蒸留水を追加した。密閉
の状態で２時間内温４０〜５０℃で反応させた後、開放
にして４０℃の乾燥器内に放置した。得られたゲル体は
透明であり、粉末Ｘ線回折でも、結晶の検出はできなか
った。Example 4 Methyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., LS-53)
0, hereinafter MTMS), distilled water was added so that the molar ratio of distilled water and MTMS was 1: 1. 10w of distilled water
For t%, 0.1N nitric acid was used as a catalyst. Initially, it is in a two-phase state, but if stirring is continued at an internal temperature of 40 to 50 ° C,
It became uniform as the hydrolysis / polycondensation reaction proceeded, and became transparent within 1 minute. After left standing in the sealed state at the same temperature for 2 days, the alcohol produced by the reaction was evaporated under reduced pressure of 80% of the theoretical amount, and further, it was adjusted to 0.
Added 25 moles of distilled water. 30 more in a sealed state
After reacting for 1 minute at the same temperature, the alcohol produced by the reaction is evaporated again under reduced pressure of 80% of the theoretical amount, and MT
0.5 mol of distilled water was added per mol of MS. After the reaction was carried out for 2 hours at an internal temperature of 40 to 50 ° C. in a sealed state, the mixture was opened and left in a dryer at 40 ° C. The obtained gel body was transparent, and crystals could not be detected by powder X-ray diffraction.
【００２２】実施例５ エチルトリエトキシシラン（信越化学工業、ＬＳ−２４
１０、以下ＥＴＥＳ）に、蒸留水とＥＴＥＳのモル比が
１．７５：１になるように蒸留水を添加した。蒸留水の
１０ｗｔ％の水は触媒として０．１Ｎの硝酸を用いた。
最初は２相の状態であるが、内温４０〜５０℃で攪拌を
続けると、加水分解・重縮合反応が進むにつれて均一に
なり、３０分間以内に透明になった。密閉の状態で同温
度で２日間静置した後、開放にして４０℃の乾燥器中に
放置した。得られたゲル体は透明であり、粉末Ｘ線回折
でも、結晶の検出はできなかった。Example 5 Ethyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., LS-24)
Distilled water was added to 10, ETES hereinafter) so that the molar ratio of distilled water to ETES was 1.75: 1. As 10 wt% of distilled water, 0.1N nitric acid was used as a catalyst.
Initially, it was in a two-phase state, but when stirring was continued at an internal temperature of 40 to 50 ° C., it became uniform as the hydrolysis / polycondensation reaction proceeded, and became transparent within 30 minutes. After left standing in the sealed state at the same temperature for 2 days, it was opened and left in a drier at 40 ° C. The obtained gel body was transparent, and crystals could not be detected by powder X-ray diffraction.
【００２３】実施例６ エチルトリエトキシシラン（信越化学工業、ＬＳ−２４
１０、以下ＥＴＥＳ）に、蒸留水とＥＴＥＳのモル比が
２．５：１になるように蒸留水を添加した。蒸留水の１
０ｗｔ％の水は触媒として０．１Ｎの硝酸を用いた。最
初は２相の状態であるが、内温４０〜５０℃で攪拌を続
けると、加水分解・重縮合反応が進むにつれて均一にな
り、３０分間以内に透明になった。密閉の状態で同温度
で２日間静置した後、開放にして４０℃の乾燥器内に放
置した。得られたゲル体は透明であり、粉末Ｘ線回折で
も、結晶の検出はできなかった。Example 6 Ethyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., LS-24)
10, hereinafter referred to as ETES), distilled water was added so that the molar ratio of distilled water and ETES was 2.5: 1. 1 of distilled water
For 0 wt% water, 0.1 N nitric acid was used as a catalyst. Initially, it was in a two-phase state, but when stirring was continued at an internal temperature of 40 to 50 ° C., it became uniform as the hydrolysis / polycondensation reaction proceeded, and became transparent within 30 minutes. After left standing in the sealed state at the same temperature for 2 days, it was opened and left in a dryer at 40 ° C. The obtained gel body was transparent, and crystals could not be detected by powder X-ray diffraction.
【００２４】実施例７ ビニルトリエトキシシラン（信越化学工業、ＬＳ−２３
００、以下ＶＴＥＳ）に、蒸留水とＶＴＥＳのモル比が
１．５：１になるように蒸留水を添加した。蒸留水の１
０ｗｔ％の水は触媒として０．１Ｎの硝酸を用いた。最
初は２相の状態であるが、内温４０〜５０℃で攪拌を続
けると、加水分解・重縮合反応が進むにつれて均一にな
り、３０分間以内に透明になった。密閉の状態で同温度
で２日間静置した後、開放にして４０℃の乾燥器内に放
置した。得られたゲル体は透明であり、粉末Ｘ線回折で
も、結晶の検出はできなかった。Example 7 Vinyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., LS-23)
00, hereinafter VTES), distilled water was added so that the molar ratio of distilled water to VTES was 1.5: 1. 1 of distilled water
For 0 wt% water, 0.1 N nitric acid was used as a catalyst. Initially, it was in a two-phase state, but when stirring was continued at an internal temperature of 40 to 50 ° C., it became uniform as the hydrolysis / polycondensation reaction proceeded, and became transparent within 30 minutes. After left standing in the sealed state at the same temperature for 2 days, it was opened and left in a dryer at 40 ° C. The obtained gel body was transparent, and crystals could not be detected by powder X-ray diffraction.
【００２５】実施例８ フェニルトリエトキシシラン（信越化学工業、ＬＳ−４
４８０、以下ＰＴＥＳ）に、蒸留水とＰＴＥＳのモル比
が１．５：１になるように蒸留水を添加した。蒸留水の
１０ｗｔ％の水は触媒として０．１Ｎの硝酸を用いた。
最初は２相の状態であるが、内温４０〜５０℃で攪拌を
続けると、加水分解・重縮合反応が進むにつれて均一に
なり、３０分間以内に透明になった。密閉の状態で同温
度で２日間静置した後、開放にして４０℃の乾燥器内に
放置した。得られたゲル体は透明であり、粉末Ｘ線回折
でも、結晶の検出はできなかった。Example 8 Phenyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., LS-4)
480, hereinafter referred to as PTES), distilled water was added so that the molar ratio of distilled water and PTES was 1.5: 1. As 10 wt% of distilled water, 0.1N nitric acid was used as a catalyst.
Initially, it was in a two-phase state, but when stirring was continued at an internal temperature of 40 to 50 ° C., it became uniform as the hydrolysis / polycondensation reaction proceeded, and became transparent within 30 minutes. After left standing in the sealed state at the same temperature for 2 days, it was opened and left in a dryer at 40 ° C. The obtained gel body was transparent, and crystals could not be detected by powder X-ray diffraction.
【００２６】比較例３ ＰＴＥＳに、蒸留水とＰＴＥＳのモル比が１．５：１に
なるように蒸留水を添加した。蒸留水の１０ｗｔ％の水
は触媒として０．１Ｎの硝酸を用いた。最初は２相の状
態であるが、内温４０〜５０℃で攪拌を続けると、加水
分解・重縮合反応が進むにつれて均一になり、３０分間
以内に透明になった。密閉の状態で室温で６ケ月間静置
したところ、溶液がゲル化せず、結晶の沈殿が認められ
た。Comparative Example 3 Distilled water was added to PTES so that the molar ratio of distilled water and PTES was 1.5: 1. As 10 wt% of distilled water, 0.1N nitric acid was used as a catalyst. Initially, it was in a two-phase state, but when stirring was continued at an internal temperature of 40 to 50 ° C., it became uniform as the hydrolysis / polycondensation reaction proceeded, and became transparent within 30 minutes. When left in a sealed state at room temperature for 6 months, the solution did not gel and precipitation of crystals was observed.
【００２７】実施例９ 実施例１で得た透明ゲル体について下記の測定を行っ
た。熱安定性についてはＤＴＡ−ＴＧで調べたところ、
４００℃付近で、放熱を伴う重量減少が見られた。４０
０℃までは、熱的に安定であった。乾燥ゲルの屈折率は
アッベ屈折率を測定したところ、１．４１２であった。Example 9 The transparent gel body obtained in Example 1 was subjected to the following measurements. The thermal stability was examined by DTA-TG,
At around 400 ° C., a weight loss accompanied by heat dissipation was observed. 40
It was thermally stable up to 0 ° C. When the Abbe refractive index was measured, the refractive index of the dried gel was 1.412.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年１２月１３日[Submission date] December 13, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項９[Name of item to be corrected] Claim 9
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１３[Correction target item name] 0013
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１３】出発原料溶液は前記オルガノトリアルコキ
シシラン、水、触媒を含んでおり、触媒としては硝酸、
塩酸等の無機酸触媒、酢酸等の有機酸触媒が常法に従っ
て使用される。The starting material solution contains the organotrialkoxysilane, water and a catalyst, and the catalyst is nitric acid,
An inorganic acid catalyst such as hydrochloric acid and an organic acid catalyst such as acetic acid are used according to a conventional method.
Claims (9)
ケイ素原子へ結合した有機基）で表わされるネットワー
ク構成単位が三次元網目構造を形成するように反復結合
しているポリシロキサンよりなる有機基含有透明シリカ
バルク体。1. A network constitutional unit represented by the formula: RSiO 3/2 (R is an organic group bonded to a silicon atom by a carbon atom) comprises a polysiloxane which is repeatedly bonded so as to form a three-dimensional network structure. Organic group-containing transparent silica bulk material.
ルク体。2. The silica bulk body according to claim 1, wherein R is a hydrocarbon group.
ピル、イソプロピル、ビニル、フェニルの内の少なくと
も１種である請求項２のシリカバルク体。3. The silica bulk body according to claim 2, wherein the hydrocarbon group is at least one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, vinyl and phenyl.
よってケイ素原子へ結合した有機基、Ｒ’は低級アルキ
ル基）のオルガノトリアルコキシシランをアルコール系
溶媒の不存在下水と反応させた後、開放系において反応
物を熟成してゲル化させることを特徴とする請求項１の
シリカバルク体を製造する方法。4. An organotrialkoxysilane of the formula: RSi (OR ') 3 (R is an organic group bonded to a silicon atom by a carbon atom, R'is a lower alkyl group) is reacted with water in the absence of an alcohol solvent. The method for producing a silica bulk body according to claim 1, wherein the reaction product is aged and gelled in an open system.
トリアルコキシシランへ、１．５≦Ｈ2 Ｏ／Ｓｉ≦３．
０（モル比）の水を添加して反応させた後、開放系にお
いて反応物を熟成してゲル化させることを特徴とする請
求項４の方法。5. To the organotrialkoxysilane containing no alcohol solvent, 1.5 ≦ H 2 O / Si ≦ 3.
The method according to claim 4, wherein 0 (molar ratio) of water is added and reacted, and then the reaction product is aged and gelled in an open system.
トリアルコキシシランへ、初回は１．０≦Ｈ2 Ｏ／Ｓｉ
＜１．５（モル比）、最終回までに初回から積算して
１．５≦Ｈ2 Ｏ／Ｓｉ≦２．０（モル比）となるように
少なくとも２回に分割して水を添加して反応させ、この
間に水の積算量が１．５≦Ｈ2 Ｏ／Ｓｉとなる以前に任
意の段階で、副生したアルコールを合計で少なくとも５
０％系外へ除去した後、開放系において反応物を熟成し
てゲル化させることを特徴とする請求項４の方法。6. The organotrialkoxysilane containing no alcoholic solvent is 1.0 ≦ H 2 O / Si for the first time.
<1.5 (molar ratio), water was added at least twice so that the total was 1.5 ≦ H 2 O / Si ≦ 2.0 (molar ratio) from the first time by the last time. At least 5 times in total at any stage before the cumulative amount of water becomes 1.5 ≦ H 2 O / Si.
The method according to claim 4, wherein the reaction product is aged and gelled in an open system after the removal to the outside of 0% system.
エチル、ｎ−プロピル、イソプロピル、ビニル、フェニ
ルの内の少なくとも１種である請求項５の方法。7. The method according to claim 5, wherein R of the organotrialkoxysilane is at least one of ethyl, n-propyl, isopropyl, vinyl and phenyl.
メチル、エチル、ｎ−プロピル、イソプロピル、ビニ
ル、フェニルの内の少なくとも１種である請求項６の方
法。8. The method according to claim 6, wherein R of the organotrialkoxysilane is at least one of methyl, ethyl, n-propyl, isopropyl, vinyl and phenyl.
の反応は、触媒量の酸または塩基の存在下で行われる請
求項４ないし８のいずれかの方法。9. The method according to claim 4, wherein the reaction between the organotrialkoxysilane and water is carried out in the presence of a catalytic amount of an acid or a base.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8749794A JPH07277760A (en) | 1994-04-01 | 1994-04-01 | Transparent bulk silica material containing organic group and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8749794A JPH07277760A (en) | 1994-04-01 | 1994-04-01 | Transparent bulk silica material containing organic group and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07277760A true JPH07277760A (en) | 1995-10-24 |
Family
ID=13916614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8749794A Pending JPH07277760A (en) | 1994-04-01 | 1994-04-01 | Transparent bulk silica material containing organic group and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07277760A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0772060A3 (en) * | 1995-11-06 | 1998-04-08 | DOW CORNING ASIA, Ltd. | Polysiloxane resin containing optically-functional constituents and transparent optically-functional element obtained therefrom |
| WO2005000943A1 (en) * | 2003-06-26 | 2005-01-06 | Central Glass Company, Limited | Organic-inorganic hybrid vitreous material and method for producing same |
| WO2005082975A1 (en) * | 2004-02-27 | 2005-09-09 | Central Glass Company, Limited | Organic-inorganic hybrid vitreous material and method for producing same |
| CN100338117C (en) * | 2003-06-26 | 2007-09-19 | 中央硝子株式会社 | Organic-inorganic hybrid vitreous material and method for producing same |
-
1994
- 1994-04-01 JP JP8749794A patent/JPH07277760A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0772060A3 (en) * | 1995-11-06 | 1998-04-08 | DOW CORNING ASIA, Ltd. | Polysiloxane resin containing optically-functional constituents and transparent optically-functional element obtained therefrom |
| WO2005000943A1 (en) * | 2003-06-26 | 2005-01-06 | Central Glass Company, Limited | Organic-inorganic hybrid vitreous material and method for producing same |
| CN100338117C (en) * | 2003-06-26 | 2007-09-19 | 中央硝子株式会社 | Organic-inorganic hybrid vitreous material and method for producing same |
| US7451619B2 (en) | 2003-06-26 | 2008-11-18 | Central Glass Company, Limited | Organic-inorganic hybrid glassy materials and their production processes |
| WO2005082975A1 (en) * | 2004-02-27 | 2005-09-09 | Central Glass Company, Limited | Organic-inorganic hybrid vitreous material and method for producing same |
| KR100756398B1 (en) * | 2004-02-27 | 2007-09-10 | 샌트랄 글래스 컴퍼니 리미티드 | Organic-inorganic hybrid vitreous material and method for producing same |
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