CN112390953B - Preparation and single crystal culture method of dodecaphenyl polyhedral silsesquioxane and single crystal - Google Patents

Preparation and single crystal culture method of dodecaphenyl polyhedral silsesquioxane and single crystal Download PDF

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CN112390953B
CN112390953B CN202011292088.0A CN202011292088A CN112390953B CN 112390953 B CN112390953 B CN 112390953B CN 202011292088 A CN202011292088 A CN 202011292088A CN 112390953 B CN112390953 B CN 112390953B
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张文超
张伟伟
杨荣杰
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Beijing Institute of Technology BIT
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Abstract

The invention relates to the technical field of organic-inorganic hybrid materials, and provides a preparation method and a single crystal culture method of dodecaphenyl polyhedral oligomeric silsesquioxane and a single crystal. According to the invention, phenyl silane is dissolved in an organic solvent, then a catalyst aqueous solution is added for hydrolysis condensation reaction, the pH value of the obtained product feed liquid is adjusted to be neutral, and then washing, standing, filtering and drying are sequentially carried out, so that the dodecaphenyl polyhedral silsesquioxane is obtained. The preparation method provided by the invention has the advantages of simple steps, easily controlled reaction conditions, simple post-treatment and no need of complex purification. The invention cultures the single crystal of the dodecaphenyl polyhedral silsesquioxane for the first time, and the provided single crystal culture method is simple and easy to implement, short in time, convenient to observe and high in yield. The single crystal obtained by the method is colorless and transparent, and has a regular shape.

Description

Preparation and single crystal culture method of dodecaphenyl polyhedral silsesquioxane and single crystal
Technical Field
The invention relates to the technical field of organic-inorganic hybrid materials, in particular to a preparation method and a single crystal culture method of dodecaphenyl polyhedral oligomeric silsesquioxane and a single crystal.
Background
Cage-shaped oligomeric silsesquioxane (POSS) is a novel organic-inorganic hybrid material, and due to designability and nanometer effect of organic groups of POSS, POSS becomes a hotspot for researches in the field of polymer modification at home and abroad in recent years. In the aspect of crystallization, POSS nano particles can play a role of nucleation sites, and when POSS participates in melt blending of polycaprolactone and polylactic acid matrixes, the crystallinity and the mechanical property of the corresponding matrixes can be greatly improved. In addition, POSS can significantly improve the crystallization rate and dynamic storage modulus of the material, and can be used as a base material for developing liquid crystals and catalysts due to the symmetrical polyhedral structure and stable chemical characteristics of the POSS.
Research shows that octaphenyl cage-shaped silsesquioxane is equivalent to the secondary structure of a crystalline silica or zeolite framework, and a material formed by the octaphenyl cage-shaped silsesquioxane has higher hardness and thermal stability; meanwhile, the octaphenyl cage-shaped silsesquioxane can form a colorless and transparent single crystal with a regular structure, and has high application value in the aspects of aerospace, electronic appliances and the like.
Phenyl polyhedral oligomeric silsesquioxane has many excellent characteristics, but the synthesis of single polyphenyl polyhedral oligomeric silsesquioxane is difficult, and particularly, the synthesis process of polyhedral oligomeric silsesquioxane with more than ten phenyl groups is complex, long in period, difficult in post-treatment, and difficult to culture to obtain high-quality single crystals.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing and growing a single crystal of dodecaphenyl polyhedral silsesquioxane and a single crystal. The preparation method of the dodecaphenyl polyhedral silsesquioxane provided by the invention has the advantages of simple steps, easily controlled preparation conditions and simple post-treatment; the single crystal culture method provided by the invention is simple, the required time is short, and the obtained single crystal has good quality.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of dodecaphenyl polyhedral silsesquioxane comprises the following steps:
dissolving phenyl silane in an organic solvent, and then adding an alkaline catalyst aqueous solution to perform a hydrolytic condensation reaction to obtain a product liquid; the temperature of the hydrolysis condensation reaction is 30-80 ℃, and the time is 12-96 h;
and adjusting the pH value of the product liquid to be neutral, and then sequentially carrying out water washing, standing, filtering and drying to obtain the dodecaphenyl polyhedral oligomeric silsesquioxane.
Preferably, the phenyl silane is phenyl trichlorosilane, phenyl trimethoxysilane or phenyl triethoxysilane.
Preferably, the organic solvent is one or more of acetone, petroleum ether, acetonitrile, dichloromethane, chloroform, pyridine and dioxane.
Preferably, the alkaline catalyst is one or more of potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide and tetraethylammonium hydroxide.
Preferably, the dosage ratio of the phenyl silane to the organic solvent is 1g (0.5-12) mL; the mass ratio of the phenyl silane to the basic catalyst is 1 (0.002-0.1); the dosage ratio of the alkaline catalyst to water in the alkaline catalyst aqueous solution is 1g (10-150) mL.
Preferably, the reagent for adjusting the pH value of the product feed liquid is acid; the volume ratio of the product material liquid to the washing water is 1 (0.05-1).
The invention also provides a single crystal culture method of the dodecaphenyl polyhedral oligomeric silsesquioxane, which comprises the following steps of:
dissolving the dodecylphenyl polyhedral oligomeric silsesquioxane prepared by the preparation method in the scheme into a volatile solvent, and volatilizing the solvent from the obtained dissolved solution under a standing condition to obtain dodecylphenyl polyhedral oligomeric silsesquioxane single crystals; the standing time is 1-5 days, and the temperature is 5-30 ℃.
Preferably, the dissolving temperature is 30-70 ℃, and the dissolving mode is ultrasonic dissolving.
Preferably, the volatile solvent is one or more of dichloromethane, toluene, diethyl ether, tetrahydrofuran, n-hexane, acetone, chloroform, acetonitrile, ethanol and methanol; the dosage ratio of the dodecaphenyl polyhedral oligomeric silsesquioxane to the volatile solvent is 1g (30-150) mL.
The invention also provides a dodecaphenyl polyhedral oligomeric silsesquioxane single crystal cultured by the culture method in the scheme, and the unit cell parameters are as follows:
Figure BDA0002784186250000021
α 90.00 °, β 90.00 °, γ 90.00 °, unit cell volume
Figure BDA0002784186250000022
The dodecaphenyl polyhedral silsesquioxane single crystal belongs to a tetragonal system, the space group is P4/n, and the dodecaphenyl polyhedral silsesquioxane single crystal is a colorless single crystal.
The invention provides a preparation method of dodecaphenyl polyhedral oligomeric silsesquioxane, which comprises the following steps: dissolving phenyl silane in an organic solvent, and then adding an alkaline catalyst aqueous solution to perform a hydrolytic condensation reaction to obtain a product liquid; the temperature of the hydrolysis condensation reaction is 30-80 ℃, and the time is 12-96 h; and adjusting the pH value of the product liquid to be neutral, and then sequentially carrying out water washing, standing, filtering and drying to obtain the dodecaphenyl polyhedral oligomeric silsesquioxane. The preparation method provided by the invention has the advantages of simple steps, easily controlled reaction conditions, simple post-treatment and no need of complex purification.
The invention also provides a single crystal culture method of the dodecaphenyl polyhedral oligomeric silsesquioxane, the single crystal of the dodecaphenyl polyhedral oligomeric silsesquioxane is obtained by the first culture, and the provided single crystal culture method is simple and easy to implement, short in time, convenient to observe and high in yield. The crystal obtained by the method is colorless and transparent, has a regular shape, provides raw material guarantee for further research and development of the dodecaphenyl polyhedral oligomeric silsesquioxane, and is suitable for the research on the stereo configuration of the dodecaphenyl polyhedral oligomeric silsesquioxane.
Drawings
FIG. 1 is a FT-IR spectrum of dodecaphenyl polyhedral silsesquioxane prepared in example 1;
FIG. 2 is an XRD spectrum of dodecaphenyl polyhedral silsesquioxane prepared in example 1;
FIG. 3 is a MALDI-TOF spectrum of dodecaphenyl polyhedral silsesquioxane prepared in example 1;
FIG. 4 is a thermal stability curve for dodecaphenyl polyhedral silsesquioxane prepared in example 1;
FIG. 5 is a photograph of a single crystal of dodecylphenyl polyhedral silsesquioxane cultured in example 1 to 3.
Detailed Description
The invention provides a preparation method of dodecaphenyl polyhedral oligomeric silsesquioxane, which comprises the following steps:
dissolving phenyl silane in an organic solvent, and then adding an alkaline catalyst aqueous solution to perform a hydrolytic condensation reaction to obtain a product liquid; the temperature of the hydrolysis condensation reaction is 30-80 ℃, and the time is 12-96 h;
and adjusting the pH value of the product liquid to be neutral, and then sequentially carrying out water washing, standing, filtering and drying to obtain the dodecaphenyl polyhedral oligomeric silsesquioxane.
The invention dissolves phenyl silane in organic solvent, then adds alkaline catalyst water solution to do hydrolysis condensation reaction, to obtain product liquid. In the present invention, the phenylsilane is preferably phenyltrichlorosilane, phenyltrimethoxysilane or phenyltriethoxysilane; the organic solvent is preferably one or more of acetone, petroleum ether, acetonitrile, dichloromethane, chloroform, pyridine and dioxane; the alkaline catalyst is one or more of potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide and tetraethylammonium hydroxide; the invention preferably uses the reaction raw materials, the solvent and the catalyst, can simplify the synthesis and post-treatment process and is beneficial to improving the conversion rate of the raw materials.
In the invention, the dosage ratio of the phenyl silane to the organic solvent is preferably 1g (0.5-12) mL, and more preferably 1g (3-10) mL; the mass ratio of the phenyl silane to the basic catalyst is preferably 1 (0.002-0.1), and more preferably 1 (0.01-0.08); the dosage ratio of the alkaline catalyst to water in the alkaline catalyst aqueous solution is preferably 1g (10-150) mL, and more preferably 1g (30-100) mL.
In the invention, the temperature of the hydrolysis condensation reaction is 30-80 ℃, preferably 40-70 ℃, more preferably 45-65 ℃, and the reaction time is 12-96 hours, preferably 12.5-72 hours, and more preferably 13-60 hours.
In the specific embodiment of the invention, preferably, the organic solvent is added into a reaction vessel, the mixture is heated to 30-80 ℃ and then added with the phenyl silane, then the alkaline catalyst aqueous solution is dropwise added into the reactor, so that the phenyl silane starts to react, and after the reaction is finished, a large amount of white precipitate is generated in the product liquid; the catalyst aqueous solution is preferably dripped within 30min, and the reaction time of the invention is counted from the completion of the dripping of the alkaline catalyst aqueous solution; in a specific embodiment of the present invention, the reaction vessel is preferably a three-neck flask with a reflux condenser, a constant pressure dropping funnel, a temperature control device, and magnetic stirring.
In the invention, in the hydrolysis condensation reaction process, a group connected to a silicon atom of phenyl silane is firstly hydrolyzed into a hydroxyl group, then two hydroxyl groups are condensed to remove one water molecule, and finally the dodecaphenyl polyhedral silsesquioxane is formed, wherein the reaction formula of the hydrolysis condensation reaction is shown as formula I:
Figure BDA0002784186250000041
after the product feed liquid is obtained, the pH value of the product feed liquid is adjusted to be neutral, and then washing, standing, filtering and drying are sequentially carried out to obtain the dodecaphenyl polyhedral oligomeric silsesquioxane. In the invention, the reagent for adjusting the pH value of the product feed liquid is preferably acid, and the acid is preferably glacial acetic acid, propionic acid or hydrochloric acid; the invention has no special requirements on the concentrations of the propionic acid and the hydrochloric acid, and can adjust the pH value of the product feed liquid to be neutral. In the invention, the neutrality is specifically that the pH value of the product feed liquid reaches 6.8-7.2, and preferably 7.
In the invention, the volume ratio of the product feed liquid to the water for washing is preferably 1 (0.05-1), and more preferably 1 (0.1-0.6); the number of times of the water washing is preferably 3, and the volume of water used each time is preferably the same.
The present invention does not require any particular means or conditions for the standing, filtration and drying, and those known to those skilled in the art can be used.
In the present invention, the dodecylphenyl polyhedral silsesquioxane obtained after drying is white powder with the molecular formula of C72H60O18Si12The chemical structural formula is shown as formula II; the dodecaphenyl polyhedral silsesquioxane has a relatively regular and stable polyhedral structure and is excellent in chemical stability and thermal stability.
Figure BDA0002784186250000051
The invention also provides a single crystal culture method of the dodecaphenyl polyhedral oligomeric silsesquioxane, which comprises the following steps of:
and dissolving the dodecaphenyl polyhedral oligomeric silsesquioxane prepared by the preparation method in the scheme into a volatile solvent, and volatilizing the solvent under the condition of standing the dissolved solution to obtain the dodecaphenyl polyhedral oligomeric silsesquioxane single crystal.
In the invention, the volatile solvent is preferably one or more of dichloromethane, toluene, diethyl ether, tetrahydrofuran, n-hexane, acetone, chloroform, acetonitrile, ethanol and methanol, and more preferably dichloromethane; the dosage ratio of the dodecaphenyl polyhedral oligomeric silsesquioxane to the volatile solvent is preferably 1g (30-150) mL, and more preferably 1g (50-100) mL.
In the invention, the dissolving temperature is preferably 30-70 ℃, more preferably 40-60 ℃, and the dissolving mode is ultrasonic dissolving; the invention has no special requirements on the ultrasonic conditions, and the ultrasonic treatment is carried out until the dodecaphenyl polyhedral oligomeric silsesquioxane powder is completely dissolved.
In the present invention, the dissolution vessel is preferably an elemental analysis bottle.
In the invention, the standing time is 1-5 days, preferably 2-4 days, and the standing temperature is 5-30 ℃, preferably 10-25 ℃. Under the standing condition, the solvent in the dissolving solution is slowly volatilized, and the dodecaphenyl polyhedral oligomeric silsesquioxane powder gradually grows into a single crystal.
The invention also provides a dodecaphenyl polyhedral oligomeric silsesquioxane single crystal cultured by the culture method in the scheme, and the unit cell parameters are as follows:
Figure BDA0002784186250000061
α 90.00 °, β 90.00 °, γ 90.00 °, unit cell volume
Figure BDA0002784186250000062
The dodecaphenyl polyhedral silsesquioxane single crystal belongs to a tetragonal system, the space group is P4/n, and the dodecaphenyl polyhedral silsesquioxane single crystal is a colorless single crystal. The dodecaphenyl polyhedral silsesquioxane single crystal obtained by the invention is colorless and transparent and has a regular shape.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1) Adding 1L of dichloromethane into a three-neck flask with a reflux condenser tube, a constant-pressure dropping funnel, a temperature control device and magnetic stirring, stirring and heating to 40 ℃, adding 396g of phenyltrimethoxysilane, dissolving 2g of potassium hydroxide into 100mL of distilled water, and slowly dropwise adding a potassium hydroxide aqueous solution into the three-neck flask for about 30 min; and reacting for 72 hours after the dropwise adding is finished to obtain a product feed liquid, wherein a large amount of white precipitates exist in the product feed liquid.
2) Dropwise adding glacial acetic acid into the product liquid obtained in the step 1) to neutrality under the stirring condition, then repeatedly washing white precipitate for three times by using distilled water, wherein the volume of the distilled water used each time is 250mL, and then sequentially standing, filtering and drying to obtain the dodecaphenyl polyhedral silsesquioxane white powder.
3) Taking 0.7g of the white powder obtained in the step 2) to place in an element analysis bottle, adding 40mL of dichloromethane, carrying out ultrasonic treatment at 50 ℃ until the dichloromethane is completely dissolved, and standing for 3 days at 25 ℃ to obtain the dodecaphenyl polyhedral silsesquioxane single crystal.
The white powder of dodecaphenyl polyhedral silsesquioxane prepared in step (2) was characterized and the results were as follows:
FIG. 1 shows the FT-IR spectrum of dodecaphenyl polyhedral silsesquioxane prepared in this example. In fig. 1: at 693cm-1In-plane deformation vibration of 730cm-1Bending vibration of C-H plane on aromatic ring at 1082cm-1The absorption peak is the absorption peak of Si-O-Si stretching vibration, 1430cm-1And 1594cm-1The absorption peak is the absorption peak of C ═ C stretching vibration in the product benzene ring, and is 3073cm-1The absorption peak of (2) is C-H stretching vibration on the aromatic ring. The analysis according to FIG. 1 can prove that the product obtained is a dodecaphenyl polyhedral silsesquioxane.
FIG. 2 is a preparation of this exampleThe XRD pattern of dodecaphenyl polyhedral silsesquioxane. As can be seen from fig. 2, the sharp peaks appearing in the figure indicate that the dodecaphenyl cage silsesquioxane has crystalline characteristics; wherein, at the position of 2 theta equal to 6.23 degrees, 7.10 degrees, 12.56 degrees and 15.62 degrees, the d-spacing is as follows
Figure BDA0002784186250000071
Figure BDA0002784186250000072
Respectively corresponding to the interplanar spacing, the molecular diagonal dimension and the molecular dimension of the dodecaphenyl polyhedral silsesquioxane.
FIG. 3 is a MALDI-TOF spectrum of dodecylphenylsilsesquioxane prepared in this example, wherein a peak M/z of 1571.8 appears in FIG. 3, corresponding to the cationization result of sodium dodecylphenylsilsesquioxane (1548+ M)Na+)。
FIG. 4 is a graph showing the thermal stability of the dodecaphenyl polyhedral silsesquioxane prepared in this example, and it can be seen from FIG. 4 that the residual mass was as high as 65.15% at 900 ℃. The thermal stability of the dodecaphenyl polyhedral oligomeric silsesquioxane prepared by the invention is excellent.
From the analysis results of FIGS. 1 to 4, it can be concluded that the synthesized product of this example is dodecylphenyl polyhedral silsesquioxane.
Example 2
1) Adding 0.8L of trichloromethane into a three-neck flask with a reflux condenser tube, a constant-pressure dropping funnel, a temperature control device and magnetic stirring, stirring and heating to 50 ℃, adding 480g of phenyltriethoxysilane, dissolving 7g of sodium hydroxide in 250mL of distilled water, slowly dropwise adding an aqueous solution of sodium hydroxide into the three-neck flask, and finishing dropping within about 30 min; and reacting for 48 hours after the dropwise adding is finished to obtain a product feed liquid, wherein a large amount of white precipitates exist in the product feed liquid.
2) Dropwise adding propionic acid into the product liquid obtained in the step 1) to neutrality under the stirring condition, repeatedly washing white precipitate for three times by using distilled water, wherein the volume of the distilled water used each time is 400mL, and then sequentially standing, filtering and drying to obtain the dodecaphenyl polyhedral silsesquioxane white powder.
3) Putting 0.6g of the white powder obtained in the step 2) into an element analysis bottle, adding 55mL of dichloromethane, carrying out ultrasonic treatment at 35 ℃ until the white powder is completely dissolved, and standing for 1 day at 20 ℃ to obtain the dodecaphenyl polyhedral silsesquioxane single crystal.
Example 3
1) Adding 1L of dichloromethane into a three-neck flask with a reflux condenser tube, a constant-pressure dropping funnel, a temperature control device and magnetic stirring, stirring and heating to 40 ℃, adding 396g of phenyltrimethoxysilane, dissolving 5.5g of potassium hydroxide into 240mL of distilled water, slowly dropwise adding a potassium hydroxide aqueous solution into the three-neck flask, and completing dripping within about 30 min; and reacting for 60 hours after the dropwise adding is finished to obtain a product feed liquid, wherein a large amount of white precipitates exist in the product feed liquid.
2) Dropwise adding glacial acetic acid into the product liquid obtained in the step 1) to be neutral under the stirring condition, repeatedly washing the white precipitate for three times by using distilled water, wherein the volume of the distilled water used each time is 400mL, and then sequentially standing, filtering and drying to obtain the dodecaphenyl polyhedral silsesquioxane white powder.
3) Taking 0.52g of the white powder obtained in the step 2) to place in an element analysis bottle, adding 50mL of dichloromethane, carrying out ultrasonic treatment at 40 ℃ until the dichloromethane is completely dissolved, and standing for 2 days at 25 ℃ to obtain the dodecaphenyl polyhedral silsesquioxane single crystal.
FT-IR, XRD, MALDI-TOF and thermogravimetric analysis were performed on the dodecaphenyl polyhedral silsesquioxanes prepared in examples 2 to 3, and the results were similar to those of example 1, indicating that the products synthesized in examples 2 to 3 were dodecaphenyl polyhedral silsesquioxanes.
FIG. 5 is a photograph showing a single crystal of dodecaphenyl polyhedral silsesquioxane cultured in examples 1 to 3, and it can be seen from FIG. 5 that the obtained single crystal is colorless and transparent and has a regular shape; the results of analyzing the unit cell parameters of the dodecaphenyl polyhedral oligomeric silsesquioxane single crystal prepared in examples 1 to 3 show that: the unit cell parameters are:
Figure BDA0002784186250000081
α 90.00 °, β 90.00 °, γ 90.00 °, unit cell volume
Figure BDA0002784186250000082
Belongs to a tetragonal system, has a space group of P4/n, and is a colorless single crystal.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (5)

1. A single crystal culture method of dodecaphenyl polyhedral oligomeric silsesquioxane is characterized by comprising the following steps of:
dissolving the dodecylphenyl polyhedral oligomeric silsesquioxane in a volatile solvent, and volatilizing the solvent from the obtained dissolved solution under a standing condition to obtain dodecylphenyl polyhedral oligomeric silsesquioxane single crystals; the standing time is 1-5 days, and the temperature is 5-30 ℃; the volatile solvent is one or more of dichloromethane, toluene, diethyl ether, tetrahydrofuran, n-hexane, acetone, trichloromethane, acetonitrile, ethanol and methanol; the dosage ratio of the dodecaphenyl polyhedral silsesquioxane to the volatile solvent is 1g (30-150) mL;
the preparation method of the dodecaphenyl polyhedral silsesquioxane comprises the following steps of:
dissolving phenyl silane in an organic solvent, and then adding an alkaline catalyst aqueous solution to perform a hydrolytic condensation reaction to obtain a product liquid; the temperature of the hydrolysis condensation reaction is 30-80 ℃, and the time is 12-96 h; the phenyl silane is phenyl trichlorosilane, phenyl trimethoxy silane or phenyl triethoxy silane;
adjusting the pH value of the product liquid to be neutral, and then sequentially carrying out water washing, standing, filtering and drying to obtain the dodecaphenyl polyhedral oligomeric silsesquioxane;
the organic solvent is one or more of acetone, petroleum ether, acetonitrile, dichloromethane, chloroform, pyridine and dioxane; the alkaline catalyst is one or more of potassium hydroxide, sodium carbonate, tetramethyl ammonium hydroxide and tetraethyl ammonium hydroxide.
2. A single crystal cultivation method as claimed in claim 1, wherein the dosage ratio of phenylsilane to organic solvent is 1g (0.5-12) mL; the mass ratio of the phenyl silane to the basic catalyst is 1 (0.002-0.1); the dosage ratio of the alkaline catalyst to water in the alkaline catalyst aqueous solution is 1g (10-150) mL.
3. A single crystal growing method according to claim 1, wherein the agent for adjusting the pH of the product feed solution is an acid; the volume ratio of the product material liquid to the washing water is 1 (0.05-1).
4. A single crystal cultivation method as claimed in claim 1, wherein the temperature at which the dodecaphenyl polyhedral silsesquioxane is dissolved is 30 to 70 ℃, and the dissolution is ultrasonic dissolution.
5. A dodecaphenyl polyhedral silsesquioxane single crystal grown by the method of any one of claims 1 to 4, wherein unit cell parameters are as follows: a =17.48 a, b =17.48 a, c =14.14 a; α =90.00o，β=90.00o，γ=90.00oUnit cell volume of 4323A3The dodecaphenyl polyhedral silsesquioxane single crystal belongs to a tetragonal system, the space group is P4/n, and the dodecaphenyl polyhedral silsesquioxane single crystal is a colorless single crystal.
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Citations (3)

* Cited by examiner, † Cited by third party
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JPS55145694A (en) * 1979-05-02 1980-11-13 Shin Etsu Chem Co Ltd Preparation of dodecaphenylsilsesquioxane
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JP2011098939A (en) * 2009-11-09 2011-05-19 Konishi Kagaku Ind Co Ltd Completely condensed oligosilsesquioxane and method for producing the same
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