CN103613610A - Vinyl hepta-phenyl silsesquioxane material and preparation method - Google Patents
Vinyl hepta-phenyl silsesquioxane material and preparation method Download PDFInfo
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Abstract
The invention discloses a vinyl hepta-phenyl silsesquioxane material. The material is prepared from the following ingredient in molar ratios, 1.0 part of T7 sodium salt hepta-polyphenyl silsesquioxane trisilicon sodium alcoholate and 1.2-2 parts of vinyl trichlorosilane. The T7 sodium salt is prepared from phenyl trimethoxy siloxane, deionized water and a first catalyst with a molar ratio of 1.0:1.1-5:0.5-2. The invention also discloses a preparation method for vinyl hepta-phenyl silsesquioxane material. The material has high yield, high purity, good stability, and good organic solubility, and can be used for preparing high-performance nanocomposites through modification of macromolecules of thermosetting resins, thermoplastic resins, rubbers and the like. The method has advantages of compact technologies, low cost, short reaction time and good product structural oneness, and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to the preparation method of compound, be specifically related to a kind of vinyl seven phenyl silsesquioxane materials and preparation method thereof.
Background technology
Cage-type silsesquioxane (POSS) is the organic-inorganic materials of a quasi-representative, also be the silicoorganic compound that a class has special three-dimensional polyhedron nanostructure, its three-dimensional dimension is in 0.7nm～50nm left and right, by inorganic " core " and organic " shell ", formed, each POSS particle contains 1-8Ge organic active functional group, these functional groups can carry out polymerization, grafting, surface bond or other reactions, are easy to carry out molecular designing, form POSS-polymer materials.POSS has organic and mineral compound character concurrently, is characterized in that it can be dissolved in solvent and resin, thereby can guarantees to realize molecularly dispersed structure, thereby can reduce viscosity, can strengthen loading level simultaneously.Because it is with the resin compatible of fusing and become one, thereby do not affect its processing fluidity.But when temperature, be down to their fusing point when following, just solidify to form nanostructure immediately and cause enhancement.Just in time contrary as for inorganic nano-particles such as nano imvites, because it can not dissolve, therefore reduced the processing fluidity of melt.POSS can be connected in the mode of chemical bonding in organic chain, therefore can form real organic/inorganic nano-hybrid materials, makes physical strength, the second-order transition temperature (T of polymer materials
g), use temperature and thermal stability all obtained large increase.
At present, the synthetic route of POSS monomer mainly contains complete hydrolysis method, partial hydrolysis-angle-sealing method, functional group's derivatization method.Complete hydrolysis method is mainly with RSi (OR)
3or RSiCl
3for raw material forms through catalyst action hydrolysis-condensation reaction in solvent.Partial hydrolysis-angle-sealing method is RSiX
3hydrolytic condensation can generate the poly-POSS of unfilled corner seven with three silicon hydroxyls under certain condition, then adds function base silane monomer in the ratio of equivalent, and further hydrolytic condensation closed loop, obtains single function base POSS.Functional group's derivatization method is to utilize existing substituent POSS, by chemical reaction (oxidation, the addition of silicon hydrogen etc.), obtains required function base POSS molecule.At present comparatively ripe about the research of eight function base POSS, but eight function base POSS existing problems aspect the level of response of solvability and polymkeric substance and consistency, make its in performance not as single function base POSS.Traditional preparation list function base POSS key is to obtain the poly-POSS(T7 of unfilled corner seven with three silicon hydroxyls), be synthetic by top band cap, the deficiency such as it exists, and processing condition are complicated, reaction time is long, the separation of product and purification difficult, productive rate are low.Octa-polysilsesquioxane and eight vinyl polysilsesquioxane techniques are very ripe, but solvability is very poor, bad with polymer-polymer miscibility.
Summary of the invention
The object of the invention is, not enough for prior art, provide the vinyl that a kind of structure unicity is good, purity is high seven phenyl silsesquioxane materials;
The present invention also provides the preparation method of the industrialization of above-mentioned materials.
The technical scheme that the present invention adopted is for achieving the above object:
A kind of vinyl seven phenyl silsesquioxane materials, it is characterized in that, it is by following component raw material: T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates, vinyl trichloro silane, the second catalyzer are made, and its mol ratio is: T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates 1.0: vinyl trichloro silane 1.2～2: the second catalyzer 0.01～0.05.
Described T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates are made by phenyl trimethoxy siloxane, deionized water, the first catalyzer, and its mol ratio is: phenyltrimethoxysila,e 1.0: deionized water 1.1～5: the first catalyzer 0.5～2.
Described the first catalyzer is one of sodium hydroxide, potassium hydroxide.
Described the second catalyzer be triethylamine, Trimethylamine 99, diethylamine, pyridine, DMF one of them.
A preparation method for described vinyl seven phenyl silsesquioxane materials, is characterized in that, it comprises the steps:
(1) by following mol ratio, take each raw material: phenyltrimethoxysila,e 1.0: deionized water 1.1～5: the first catalyzer 0.5～2;
(2) phenyltrimethoxysila,e step (1) being weighed, deionized water, the first catalyzer mix in being equipped with the flask of prolong, and add 250ml the first solvent dispersion to mix;
(3) by step (2) mixing solutions, return stirring 4～10h in oil bath under 50～80 ℃ of conditions, room temperature to be naturally cooled to, under magnetic agitation, continue reaction 10～25h, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 ℃ of conditions of vacuum, dry 24h, draws head product T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates;
(4) by prepared T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates of step (3) under argon shield, add again following raw material, vinyl trichloro silane, the second catalyzer, its mol ratio is: T7 sodium salt 1.0: vinyl trichloro silane 1.2～2: the second catalyzer 0.01～0.05;
(5) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates that step (4) weighed are dispersed in 250～500ml the second solvent, then add the second catalyzer, vinyl trichloro silane;
(6) by step (5) mixing solutions, at-10 ℃～10 ℃ ice-water bath condition lower magnetic forces, stir 3h～15h, room temperature to be returned back to continues to react 3h～15h under magnetic agitation; Add deionized water stopped reaction, separate organic phase, wash 3 times, anhydrous magnesium sulfate drying, filters and removes siccative, again filtrate is added in 1000～2000ml the 3rd solvent, separate out white solid, suction filtration, then use the 3rd solvent wash 3 times, under 60 ℃ of vacuum conditions, be dried 24h, draw vinyl seven phenyl silsesquioxane materials.
Described the first catalyzer is one of them of sodium hydroxide, potassium hydroxide.
Described the second catalyzer is one of them of triethylamine, Trimethylamine 99, diethylamine, pyridine, DMF.
Described the first solvent be THF, methyl alcohol, ethanol, Virahol one of them.
Described the second solvent be THF, toluene, benzene, ethers one of them.
Described the 3rd solvent be methyl alcohol, ethanol, isopropyl alcohols, sherwood oil one of them.
The invention has the beneficial effects as follows: vinyl seven phenyl silsesquioxane materials provided by the invention, structure unicity is good, productive rate is high, purity is high, good stability, include the POSS monomer that structure is clear and definite, organic-dissolvable is good, have broad application prospects, can be for macromolecule modified high-performance nano matrix materials of preparing such as thermosetting resin, thermoplastic resin and rubber.
Preparation method provided by the invention, its technique is compact, and cost is low, reaction times is short, and prepared product structure unicity is good, and productive rate is high, purity is high, good stability, has the POSS monomer that structure is clear and definite in product, the prepared product structure unicity of present method is good, productive rate is high, purity is high, and good stability can be mass-produced.
Below in conjunction with accompanying drawing and embodiment, invention is further illustrated.
Accompanying drawing explanation
Fig. 1 is the SEM figure of vinyl seven phenyl silsesquioxanes;
Fig. 2 is vinyl seven phenyl silsesquioxanes
1h NMR and
13c NMR figure.
Embodiment
Embodiment 1: referring to Fig. 1～Fig. 2, the vinyl seven phenyl silsesquioxane materials that the present embodiment provides, it is made by following feed composition: T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates, vinyl trichloro silane, the second catalyzer, its mol ratio is: T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates 1.0: vinyl trichloro silane 1.2～2: the second catalyzer 0.01～0.05.
Described T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates are made by phenyl trimethoxy siloxane, deionized water, the first catalyzer, and its mol ratio is: phenyltrimethoxysila,e 1.0: deionized water 1.1～5: the first catalyzer 0.5～2.
Described the first catalyzer is one of sodium hydroxide, potassium hydroxide.
Described the second catalyzer is one of them of triethylamine, Trimethylamine 99, diethylamine, pyridine, DMF.
A preparation method for described vinyl seven phenyl silsesquioxane materials, it comprises the steps:
(1) by following mol ratio, take each raw material: phenyltrimethoxysila,e 1.0: deionized water 1.1～5: the first catalyzer 0.5～2;
(2) phenyltrimethoxysila,e step (1) being weighed, deionized water, the first catalyzer mix in being equipped with the flask of prolong, and add 250ml the first solvent dispersion to mix;
(3) by step (2) mixing solutions, return stirring 4～10h in oil bath under 50～80 ℃ of conditions, room temperature to be naturally cooled to, under magnetic agitation, continue reaction 10～25h, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 ℃ of conditions of vacuum, dry 24h, draws head product T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates;
(4) by prepared T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates of step (3) under argon shield, add again following raw material, vinyl trichloro silane, the second catalyzer, its mol ratio is: T7 sodium salt 1.0: vinyl trichloro silane 1.2～2: the second catalyzer 0.01～0.05;
(5) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates that step (4) weighed are dispersed in 250～500ml the second solvent, then add the second catalyzer, vinyl trichloro silane;
(6) by step (5) mixing solutions, at-10 ℃～10 ℃ ice-water bath condition lower magnetic forces, stir 3h～15h, room temperature to be returned back to continues to react 3h～15h under magnetic agitation; Add deionized water stopped reaction, separate organic phase, wash 3 times, anhydrous magnesium sulfate drying, filters and removes siccative, again filtrate is added in 1000～2000ml the 3rd solvent, separate out white solid, suction filtration, then use the 3rd solvent wash 3 times, under 60 ℃ of vacuum conditions, be dried 24h, draw vinyl seven phenyl silsesquioxane materials.
Described the first catalyzer is one of them of sodium hydroxide, potassium hydroxide.
Described the second catalyzer is one of them of triethylamine, Trimethylamine 99, diethylamine, pyridine, DMF.
Described the first solvent be THF, methyl alcohol, ethanol, Virahol one of them.
Described the second solvent be THF, toluene, benzene, ethers one of them.
Described the 3rd solvent be methyl alcohol, ethanol, isopropyl alcohols, sherwood oil one of them.
Embodiment 2: vinyl seven phenyl silsesquioxane materials that the present embodiment provides and preparation method thereof, and its feed composition and step are all substantially the same manner as Example 1, and its difference is:
The preparation method of these vinyl seven phenyl silsesquioxane materials, it comprises the following steps:
(1) by following each raw material of molar ratio weighing: phenyltrimethoxysila,e 1.0: deionized water 1.1: sodium hydroxide 0.5;
(2) phenyltrimethoxysila,e step (1) being weighed, deionized water, sodium hydroxide mix in being equipped with the flask of prolong, and add 250mlTHF dispersing and mixing;
(3) by step (2) mixing solutions, return stirring 10h in oil bath under 50 ℃ of conditions, room temperature to be naturally cooled to, under magnetic agitation, continue reaction 25h, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 ℃ of conditions of vacuum, dry 24h, draws head product T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates;
(4) by prepared T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates of step (3) under argon shield, add again following raw material, vinyl trichloro silane, triethylamine, its mol ratio is: T7 sodium salt 1.0: vinyl trichloro silane 1.2: triethylamine 0.01;
(5) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates that step (4) weighed are dispersed in 250ml THF, will add triethylamine, vinyl trichloro silane to mix again;
(6) by step (5) mixing solutions, at-10 ℃ of ice-water bath condition lower magnetic forces, stir 15h, room temperature to be returned back to continues to react 15h under magnetic agitation; Add deionized water stopped reaction, separate organic phase, wash 3 times, anhydrous magnesium sulfate drying, filters and removes siccative, filtrate is added in 1000ml methyl alcohol again, separate out white solid, suction filtration, then use methanol wash 3 times, under 60 ℃ of conditions of vacuum, be dried 24h, draw vinyl seven phenyl silsesquioxane materials.
Embodiment 3: vinyl seven phenyl silsesquioxane materials that the present embodiment provides and preparation method thereof, and its step and feed composition are all basic identical with embodiment 1,2, and its difference is:
The preparation method of described vinyl seven phenyl silsesquioxane materials, it comprises the following steps:
(1) by following each raw material of molar ratio weighing: phenyltrimethoxysila,e 1.0: deionized water 5.0: potassium hydroxide 2.0;
(2) phenyltrimethoxysila,e step (1) being weighed, deionized water, potassium hydroxide mix in being equipped with the flask of prolong, and add 500ml methyl alcohol dispersing and mixing;
(3) by step (2) mixing solutions, return stirring 4h in oil bath under 80 ℃ of conditions, room temperature to be naturally cooled to, under magnetic agitation, continue reaction 10h, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 ℃ of conditions of vacuum, dry 24h, draws head product T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates;
(4) by prepared T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates of step (3) under argon shield, add again following raw material, vinyl trichloro silane, Trimethylamine 99, its mol ratio is: T7 sodium salt 1.0: vinyl trichloro silane 2.0: Trimethylamine 99 0.05;
(5) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates that step (4) weighed are dispersed in 500ml toluene, will add Trimethylamine 99, vinyl trichloro silane to mix again;
(6) by step (5) mixing solutions, at 10 ℃ of ice-water bath condition lower magnetic forces, stir 3h, room temperature to be returned back to continues to react 3h under magnetic agitation; Add deionized water stopped reaction, separate organic phase, wash 3 times, anhydrous magnesium sulfate drying, filters and removes siccative, filtrate is added in 2000ml methyl alcohol again, separate out white solid, suction filtration, then use methanol wash 3 times, under 60 ℃ of conditions of vacuum, be dried 24h, draw vinyl seven phenyl silsesquioxane materials.
Embodiment 4: vinyl seven phenyl silsesquioxane materials that the present embodiment provides and preparation method thereof, and its step and feed composition are all basic identical with embodiment 1,2,3, and its difference is:
The preparation method of described vinyl seven phenyl silsesquioxane materials, it comprises the following steps:
(1) by following each raw material of molar ratio weighing: phenyltrimethoxysila,e 1.0: deionized water 3.0: sodium hydroxide 1.3;
(2) phenyltrimethoxysila,e step (1) being weighed, deionized water, sodium hydroxide mix in being equipped with the flask of prolong, and add 250ml ethanol dispersing and mixing;
(3) by step (2) mixing solutions, return stirring 7h in oil bath under 65 ℃ of conditions, room temperature to be naturally cooled to, under magnetic agitation, continue reaction 18h, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 ℃ of conditions of vacuum, dry 24h, draws head product T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates;
(4) by prepared T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates of step (3) under argon shield, add again following raw material, vinyl trichloro silane, diethylamine, its mol ratio is: T7 sodium salt 1.0: vinyl trichloro silane 1.6: diethylamine 0.03;
(5) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates that step (4) weighed are dispersed in 350ml benzene, will add diethylamine, vinyl trichloro silane to mix again;
(6) by step (5) mixing solutions, at 0 ℃ of ice-water bath condition lower magnetic force, stir 9h, room temperature to be returned back to continues to react 9h under magnetic agitation; Add deionized water stopped reaction, separate organic phase, wash 3 times, anhydrous magnesium sulfate drying, filters and removes siccative, filtrate is added in 1500ml ethanol again, separate out white solid, suction filtration, then use washing with alcohol 3 times, under 60 ℃ of conditions of vacuum, be dried 24h, draw vinyl seven phenyl silsesquioxane materials.
Embodiment 5: vinyl seven phenyl silsesquioxane materials that the present embodiment provides and preparation method thereof, and its step and feed composition are all basic identical with one of embodiment 1,2,3,4, and its difference is:
The preparation method of described vinyl seven phenyl silsesquioxane materials, it comprises the following steps:
(1) by following each raw material of molar ratio weighing: phenyltrimethoxysila,e 1.0: deionized water 1.1: sodium hydroxide 2.0;
(2) phenyltrimethoxysila,e step (1) being weighed, deionized water, sodium hydroxide mix in being equipped with the flask of prolong, and add 250ml Virahol dispersing and mixing;
(3) by step (2) mixing solutions, return stirring 10h in oil bath under 50 ℃ of conditions, room temperature to be naturally cooled to, under magnetic agitation, continue reaction 25h, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 ℃ of conditions of vacuum, dry 24h, draws head product T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates;
(4) by prepared T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates of step (3) under argon shield, then add following raw material, vinyl trichloro silane, pyridine, its mol ratio is: T7 sodium salt 1.0: vinyl trichloro silane 1.2: pyridine 0.05;
(5) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates that step (4) weighed are dispersed in 250ml ethers, will add pyridine, vinyl trichloro silane to mix again;
(6) by step (5) mixing solutions, at-10 ℃ of ice-water bath condition lower magnetic forces, stir 15h, room temperature to be returned back to continues to react 15h under magnetic agitation; Add deionized water stopped reaction, separate organic phase, wash 3 times, anhydrous magnesium sulfate drying, filters and removes siccative, filtrate is added in 1000ml Virahol again, separate out white solid, suction filtration, then use washed with isopropyl alcohol 3 times, under 60 ℃ of conditions of vacuum, be dried 24h, draw vinyl seven phenyl silsesquioxane materials.
Embodiment 6: vinyl seven phenyl silsesquioxane materials that the present embodiment provides and preparation method thereof, and its step and feed composition are all basic identical with one of embodiment 1,2,3,4,5, and its difference is:
The preparation method of described vinyl seven phenyl silsesquioxane materials, it comprises the following steps:
(1) by following each raw material of molar ratio weighing: phenyltrimethoxysila,e 1.0: deionized water 5.0: sodium hydroxide 0.5;
(2) phenyltrimethoxysila,e step (1) being weighed, deionized water, sodium hydroxide mix in being equipped with the flask of prolong, and add 500mlTHF dispersing and mixing;
(3) by step (2) mixing solutions, return stirring 4h in oil bath under 80 ℃ of conditions, room temperature to be naturally cooled to, under magnetic agitation, continue reaction 10h, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 ℃ of conditions of vacuum, dry 24h, draws head product T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates;
(4) by prepared T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates of step (3) under argon shield, then add following raw material, vinyl trichloro silane, DMF, its mol ratio is: T7 sodium salt 1.0: vinyl trichloro silane 2.0:DMF0.01;
(5) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates that step (4) weighed are dispersed in 500ml THF, will add DMF, vinyl trichloro silane to mix again;
(6) by step (5) mixing solutions, at 10 ℃ of ice-water bath condition lower magnetic forces, stir 3h, room temperature to be returned back to continues to react 3h under magnetic agitation; Add deionized water stopped reaction, separate organic phase, wash 3 times, anhydrous magnesium sulfate drying, filters and removes siccative, filtrate is added in 2000ml sherwood oil again, separate out white solid, suction filtration, then use petroleum ether 3 times, under 60 ℃ of conditions of vacuum, be dried 24h, draw vinyl seven phenyl silsesquioxane materials.
As shown in Figure 1, in vinyl seven phenyl silsesquioxane SEM pictures prepared by above-described embodiment, its microscopic appearance is petal-shaped structure; Be illustrated in figure 2 vinyl seven phenyl silsesquioxanes
1h NMR and
13c NMR figure, can find out that from nuclear magnetic spectrum its purity can reach more than 95%.
Material provided by the invention, its product structure unicity is good, productive rate is high, purity is high, good stability, the POSS monomer that the clear and definite organic-dissolvable of structure is good, can be mass-produced, possess wide application prospect, can be for macromolecule modified high-performance nano matrix materials of preparing such as thermosetting resin, thermoplastic resin and rubber.
Preparation method's technique provided by the invention is reasonable, and cost is low, and the reaction times is short, and product structure unicity is good, easily controls, and productive rate is high, is convenient to realize industrialization; Prepared product purity is high, good stability.
The foregoing is only better possible embodiments of the present invention, not in order to limit to the scope of the claims of the present invention, therefore the equivalent structure that all utilizations specification sheets of the present invention and accompanying drawing content are done changes, be all included in protection scope of the present invention.
Claims (10)
1. vinyl seven phenyl silsesquioxane materials, is characterized in that, its feed composition by following mol ratio is made: T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates 1.0: vinyl trichloro silane 1.2～2: the second catalyzer 0.01～0.05.
2. vinyl seven phenyl silsesquioxane materials according to claim 1, it is characterized in that, described T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates are made by phenyl trimethoxy siloxane, deionized water, the first catalyzer, and its mol ratio is: phenyltrimethoxysila,e 1.0: deionized water 1.1～5: the first catalyzer 0.5～2.
3. vinyl seven phenyl silsesquioxane materials according to claim 2, is characterized in that, described the first catalyzer is one of sodium hydroxide, potassium hydroxide.
4. vinyl seven phenyl silsesquioxane materials according to claim 1, is characterized in that, described the second catalyzer be triethylamine, Trimethylamine 99, diethylamine, pyridine, DMF one of them.
5. a preparation method for vinyl seven phenyl silsesquioxane materials described in claim 1～4, is characterized in that, it comprises the steps:
(1) by following mol ratio, take each raw material: phenyltrimethoxysila,e 1.0: deionized water 1.1～5: the first catalyzer 0.5～2;
(2) phenyltrimethoxysila,e step (1) being weighed, deionized water, the first catalyzer mix in being equipped with the flask of prolong, and add 250ml the first solvent dispersion to mix;
(3) by step (2) mixing solutions, return stirring 4～10h in oil bath under 50～80 ℃ of conditions, room temperature to be naturally cooled to, under magnetic agitation, continue reaction 10～25h, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 ℃ of conditions of vacuum, dry 24h, draws head product T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates;
(4) by prepared T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates of step (3) under argon shield, add again following raw material, vinyl trichloro silane, the second catalyzer, its mol ratio is: T7 sodium salt 1.0: vinyl trichloro silane 1.2～2: the second catalyzer 0.01～0.05;
(5) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates that step (4) weighed are dispersed in 250～500 ml the second solvents, then add the second catalyzer, vinyl trichloro silane;
(6) by step (5) mixing solutions ,-10oC～10oC ice-water bath condition lower magnetic force stirring 3h～15h, room temperature to be returned back to continues to react 3h～15h under magnetic agitation; Add deionized water stopped reaction, separate organic phase, wash 3 times, anhydrous magnesium sulfate drying, filters and removes siccative, again filtrate is added in 1000～2000ml the 3rd solvent, separate out white solid, suction filtration, then use the 3rd solvent wash 3 times, under 60 ℃ of vacuum conditions, be dried 24h, draw vinyl seven phenyl silsesquioxane materials.
6. the preparation method of vinyl seven phenyl silsesquioxane materials according to claim 5, is characterized in that, described the first catalyzer is one of them of sodium hydroxide, potassium hydroxide.
7. the preparation method of vinyl seven phenyl silsesquioxane materials according to claim 5, is characterized in that, described the second catalyzer is one of them of triethylamine, Trimethylamine 99, diethylamine, pyridine, DMF.
8. the preparation method of vinyl seven phenyl silsesquioxane materials according to claim 5, is characterized in that, described the first solvent be THF, methyl alcohol, ethanol, Virahol one of them.
9. the preparation method of vinyl seven phenyl silsesquioxane materials according to claim 5, is characterized in that, described the second solvent be THF, toluene, benzene, ethers one of them.
10. the preparation method of vinyl seven phenyl silsesquioxane materials according to claim 5, is characterized in that, described the 3rd solvent be methyl alcohol, ethanol, isopropyl alcohols, sherwood oil one of them.
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Cited By (5)
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| CN103992347A (en) * | 2014-05-06 | 2014-08-20 | 上海大学 | Epoxy heptaphenyl silsesquioxane material and preparation method thereof |
| CN104262385A (en) * | 2014-03-06 | 2015-01-07 | 上海大学 | Synthesis method of monofunctional heptaphenyl silsesquioxane |
| CN108129662A (en) * | 2017-12-22 | 2018-06-08 | 中科院广州化学有限公司 | A kind of bifunctional base T10 cage-type silsesquioxanes containing phenyl and preparation method thereof |
| CN109735203A (en) * | 2018-12-25 | 2019-05-10 | 陕西科技大学 | A kind of semiclosed caged trifunctional epoxy ether POSS combination material, coating and preparation method |
| CN114874443A (en) * | 2022-06-17 | 2022-08-09 | 中国科学院长春应用化学研究所 | Silicon rubber with low curing shrinkage rate and preparation method thereof |
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| US20040030084A1 (en) * | 2002-08-06 | 2004-02-12 | Yoshitaka Morimoto | Production process for silsesquioxane derivative and silsesquioxane derivative |
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| US20040030084A1 (en) * | 2002-08-06 | 2004-02-12 | Yoshitaka Morimoto | Production process for silsesquioxane derivative and silsesquioxane derivative |
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