CN103992347A - Epoxy heptaphenyl silsesquioxane material and preparation method thereof - Google Patents
Epoxy heptaphenyl silsesquioxane material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an epoxy heptaphenyl silsesquioxane material prepared from the following components according to the molar ratio: 1.0 of alkylene heptaphenyl silsesquioxane, and 1.2-2 of m-chloroperoxybenzoic acid; the alkylene heptaphenyl silsesquioxane is prepared from T7 sodium salt heptapolyphenyl silsesquioxane sodium trisilanolate, alkylene trichloro silane and a second catalyst according to the molar ratio of 1.0:1.2-2:0.01-0.05; the T7 sodium salt heptapolyphenyl silsesquioxane sodium trisilanolate is prepared from phenyl trimethoxy siloxane, deionized water and a first catalyst according to the molar ratio of 1.0:1.1-5:0.5-2. The invention also discloses a preparation method of the epoxy heptaphenyl silsesquioxane material. The material provided by the invention has the advantages of high yield, high purity, good stability and good organic solubility, and can be used for modification of thermosetting resin, thermoplastic resin, rubber and other polymers to prepare high-performance nanocomposite materials; and the method has the advantages of compact process, low cost and short reaction time.
Description
Technical field
The present invention relates to the preparation method of compound, be specifically related to a kind of epoxy group(ing) 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, formed by inorganic " core " and organic " shell ", each POSS particle contains 1-8 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, can strengthen loading level thereby can reduce viscosity simultaneously.Because it is with the resin compatible of fusing and become one, thereby do not affect its processing fluidity.But in the time that temperature is down to below their fusing point, 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 reduce the processing fluidity of melt.POSS can be connected in organic chain in the mode of chemical bonding, 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, obtains required function base POSS molecule by chemical reaction (oxidation, the addition of silicon hydrogen etc.).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 complexity, reaction time are 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, for prior art deficiency, provide the epoxy group(ing) 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 epoxy group(ing) seven phenyl silsesquioxane materials, is characterized in that, it is by following component raw material: alkylene seven phenyl silsesquioxanes 1.0: metachloroperbenzoic acid 1.2 ~ 2;
Described alkylene seven phenyl silsesquioxanes are made up of T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates, alkylene trichlorosilane, the second catalyzer, and its mol ratio is: T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates 1.0: alkylene trichlorosilane the 1.2 ~ 2: second catalyzer 0.01 ~ 0.05.
Described T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates are made up of 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 epoxy group(ing) seven phenyl silsesquioxane materials, is characterized in that, it comprises the steps:
(1) take each raw material by following mol ratio: phenyltrimethoxysila,e 1.0: deionized water 1.1 ~ 5: the first catalyzer 0.5 ~ 2;
(2) phenyltrimethoxysila,e, deionized water, the first catalyzer that step (1) are weighed mix in the flask that is equipped with prolong, and add 250ml the first solvent dispersion to mix;
(3) by step (2) mixing solutions, return stirring 4 ~ 10 h in oil bath under 50 ~ 80 DEG C 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 DEG C of conditions of vacuum, dry 24h, draws head product T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates;
(4) by prepared step (3) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates under argon shield, add again following raw material, alkylene trichlorosilane, the second catalyzer, its mol ratio is: T7 sodium salt 1.0: alkylene trichlorosilane the 1.2 ~ 2: 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, alkylene trichlorosilane;
(6) by step (5) mixing solutions ,-10
oc ~ 10
oc ice-water bath condition lower magnetic force stirs 3h ~ 15h, and 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 DEG C of vacuum conditions, be dried 24h, draw alkylene seven phenyl silsesquioxane materials.
(7) by prepared step (6) alkylene seven phenyl silsesquioxanes under argon shield, add again following raw material, alkylene seven phenyl silsesquioxanes, metachloroperbenzoic acid, its mol ratio is: alkylene seven phenyl silsesquioxanes 1.0: metachloroperbenzoic acid 1.2 ~ 2;
(8) alkylene seven phenyl silsesquioxanes that step (7) weighed are dispersed in 40 ~ 50ml the 4th solvent, then add metachloroperbenzoic acid;
(9) by step (8) mixing solutions return stirring 2 days in oil bath under 40 ~ 45 DEG C of conditions, room temperature to be naturally cooled to, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 DEG C of conditions of vacuum, dry 24h, draws head product epoxy group(ing) seven phenyl silsesquioxanes.
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.
Described the 4th solvent be methylene dichloride, chloroform, THF one of them.
The invention has the beneficial effects as follows: epoxy group(ing) 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 compactness, 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.
Brief description of the drawings
Fig. 1 is the SEM figure of epoxy group(ing) seven phenyl silsesquioxanes;
Fig. 2 is epoxy group(ing) seven phenyl silsesquioxanes
1h NMR figure.
Embodiment
Below in conjunction with accompanying drawing and embodiment, invention is further illustrated.
embodiment 1:referring to Fig. 1 ~ Fig. 2, the epoxy group(ing) seven phenyl silsesquioxane materials that the present embodiment provides, it is by following component raw material: alkylene seven phenyl silsesquioxanes, metachloroperbenzoic acid are made, and its mol ratio is alkylene seven phenyl silsesquioxanes 1.0: metachloroperbenzoic acid 1.2.
Described alkylene seven phenyl are made up of T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates, vinyl trichloro silane, the second catalyst of triethylamine for half siloxanes, and its mol ratio is: T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates 1.0: 1.2: the second catalyst of triethylamine 0.01 of alkylene trichlorosilane
Described T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates are made up of phenyl trimethoxy siloxane, deionized water, the first catalyzer sodium hydroxide, and its mol ratio is: phenyltrimethoxysila,e 1.0: 1.1: the first catalyzer sodium hydroxide 0.5 of deionized water.
Preparation method's step of described epoxy group(ing) seven phenyl silsesquioxane materials is as follows:
(1) take each raw material by following mol ratio: phenyltrimethoxysila,e 1.0: 1.1: the first catalyzer sodium hydroxide 0.5 of deionized water;
(2) phenyltrimethoxysila,e, deionized water, the first catalyzer sodium hydroxide that step (1) are weighed mix in the flask that is equipped with prolong, and add 250ml the first solvent dispersion to mix;
(3) by step (2) mixing solutions, return stirring 4 ~ 10 h in oil bath under 60 DEG C of conditions, room temperature to be naturally cooled to, under magnetic agitation, continue reaction 15h, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 DEG C of conditions of vacuum, dry 24h, draws head product T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates;
(4) by prepared step (3) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates under argon shield, add again following raw material, vinyl trichloro silane, the second catalyst of triethylamine, its mol ratio is: T7 sodium salt 1.0: 1.2: the second catalyzer 0.02 of vinyl trichloro silane;
(5) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates that step (4) weighed are dispersed in 250 ~ 500 ml the second solvent THF, then add the second catalyst of triethylamine, vinyl trichloro silane;
(6) by step (5) mixing solutions ,-10
oc ~ 10
oc ice-water bath condition lower magnetic force stirs 8h, and room temperature to be returned back to continues to react 10h 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 the molten sherwood oil agent of 1000 ~ 2000ml the 3rd, separate out white solid, suction filtration, then use the 3rd solvent petroleum ether 3 times, under 60 DEG C of vacuum conditions, be dried 24h, draw vinyl seven phenyl silsesquioxane materials.
(7) by prepared step (6) alkylene seven phenyl silsesquioxanes under argon shield, add again following raw material, alkylene seven phenyl silsesquioxanes, metachloroperbenzoic acid, its mol ratio is: alkylene seven phenyl silsesquioxanes 1.0: metachloroperbenzoic acid 1.2;
(8) alkylene seven phenyl silsesquioxanes that step (7) weighed are dispersed in 50ml the 4th methylene chloride, then add metachloroperbenzoic acid;
(9) by step (8) mixing solutions return stirring 2 days in oil bath under 40 ~ 50 DEG C of conditions, room temperature to be naturally cooled to, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 DEG C of conditions of vacuum, dry 24h, draws head product epoxy group(ing) seven phenyl silsesquioxanes.
embodiment 2:epoxy group(ing) seven phenyl silsesquioxane materials that the present embodiment provides and preparation method thereof, its component step and suddenly all substantially the same manner as Example 1, its difference is:
The preparation method of described epoxy group(ing) seven phenyl silsesquioxane materials, it comprises the following steps:
(1) take each raw material by following mol ratio: phenyltrimethoxysila,e 1.0: deionized water 1.2: sodium hydroxide 1.0;
(2) phenyltrimethoxysila,e, deionized water, the sodium hydroxide that step (1) are weighed mix in the flask that is equipped with prolong, and add 250ml THF dispersing and mixing;
(3) by step (2) mixing solutions, return stirring 5 h in oil bath under 70 DEG C of conditions, room temperature to be naturally cooled to, under magnetic agitation, continue reaction 15h, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 DEG C of conditions of vacuum, dry 24h, draws head product T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates;
(4) by prepared step (3) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates under argon shield, add again following raw material, vinyl trichloro silane, triethylamine, its mol ratio is: T7 sodium salt 1.0: vinyl trichloro silane 1.4: triethylamine 0.05;
(5) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates that step (4) weighed are dispersed in 250ml toluene, then add triethylamine, vinyl trichloro silane;
(6) by step (5) mixing solutions, 0
oc ice-water bath condition lower magnetic force stirs 5h, and room temperature to be returned back to continues to react 10h 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 1000ml methyl alcohol, separate out white solid, suction filtration, then use the 3rd solvent wash 3 times, under 60 DEG C of vacuum conditions, be dried 24h, draw vinyl seven phenyl silsesquioxane materials.
(7) by prepared step (6) vinyl seven phenyl silsesquioxanes under argon shield, add again following raw material, vinyl seven phenyl silsesquioxanes, metachloroperbenzoic acid, its mol ratio is: vinyl seven phenyl silsesquioxanes 1.0: metachloroperbenzoic acid 2;
(8) vinyl seven phenyl silsesquioxanes that step (7) weighed are dispersed in 50ml methylene dichloride, then add metachloroperbenzoic acid;
(9) by step (8) mixing solutions return stirring 2 days in oil bath under 45 DEG C of conditions, room temperature to be naturally cooled to, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 DEG C of conditions of vacuum, dry 24h, draws head product epoxy group(ing) seven phenyl silsesquioxanes.
embodiment 3:epoxy group(ing) seven phenyl silsesquioxane materials that the present embodiment provides and preparation method thereof, its step and component are all basic identical with embodiment 1,2, and its difference is:
The preparation method of described epoxy group(ing) seven phenyl silsesquioxane materials, it comprises the following steps:
(1) take each raw material by following mol ratio: phenyltrimethoxysila,e 1.0: deionized water 1.5: sodium hydroxide 2.0;
(2) phenyltrimethoxysila,e, deionized water, the sodium hydroxide that step (1) are weighed mix in the flask that is equipped with prolong, and add 250ml Virahol dispersing and mixing;
(3) by step (2) mixing solutions, return stirring 5 h in oil bath under 80 DEG C 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 DEG C of conditions of vacuum, dry 24h, draws head product T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates;
(4) by prepared step (3) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates under argon shield, add again following raw material, vinyl trichloro silane, diethylamine, its mol ratio is: T7 sodium salt 1.0: vinyl trichloro silane 2: diethylamine 0.05;
(5) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates that step (4) weighed are dispersed in 250 ml THF, then add diethylamine, vinyl trichloro silane;
(6) by step (5) mixing solutions ,-5
oc ice-water bath condition lower magnetic force stirs 10h, and 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, again filtrate is added in 1500ml sherwood oil, separate out white solid, suction filtration, then use petroleum ether 3 times, under 60 DEG C of vacuum conditions, be dried 24h, draw vinyl seven phenyl silsesquioxane materials.
(7) by prepared step (6) vinyl seven phenyl silsesquioxanes under argon shield, add again following raw material, vinyl seven phenyl silsesquioxanes, metachloroperbenzoic acid, its mol ratio is: vinyl seven phenyl silsesquioxanes 1.0: metachloroperbenzoic acid 2;
(8) vinyl seven phenyl silsesquioxanes that step (7) weighed are dispersed in 50ml trichloromethane, then add metachloroperbenzoic acid;
(9) by step (8) mixing solutions return stirring 2 days in oil bath under 50 DEG C of conditions, room temperature to be naturally cooled to, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 DEG C of conditions of vacuum, dry 24h, draws head product epoxy group(ing) seven phenyl silsesquioxanes.
embodiment 4:epoxy group(ing) seven phenyl silsesquioxane materials that the present embodiment provides and preparation method thereof, its step and component are all basic identical with embodiment 1,2,3, and its difference is:
The preparation method of described epoxy group(ing) seven phenyl silsesquioxane materials, it comprises the following steps:
(1) take each raw material by following mol ratio: phenyltrimethoxysila,e 1.0: deionized water 1.5: potassium hydroxide 2;
(2) phenyltrimethoxysila,e, deionized water, the potassium hydroxide that step (1) are weighed mix in the flask that is equipped with prolong, and add 250ml THF dispersing and mixing;
(3) by step (2) mixing solutions, return stirring 10 h in oil bath under 75 DEG C of conditions, room temperature to be naturally cooled to, under magnetic agitation, continue reaction 15h, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 DEG C of conditions of vacuum, dry 24h, draws head product T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates;
(4) by prepared step (3) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates under argon shield, add again following raw material, allyltrichlorosilane, triethylamine, its mol ratio is: T7 sodium salt 1.0: allyltrichlorosilane 1.5: triethylamine 0.05;
(5) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates that step (4) weighed are dispersed in 300 ml THF, then add triethylamine, allyltrichlorosilane;
(6) by step (5) mixing solutions, 0
oc ice-water bath condition lower magnetic force stirs 15h, and 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, again filtrate is added in 2000ml methyl alcohol, separate out white solid, suction filtration, then use methanol wash 3 times, under 60 DEG C of vacuum conditions, be dried 24h, draw allyl group seven phenyl silsesquioxane materials.
(7) by prepared step (6) allyl group seven phenyl silsesquioxanes under argon shield, add again following raw material, allyl group seven phenyl silsesquioxanes, metachloroperbenzoic acid, its mol ratio is: allyl group seven phenyl silsesquioxanes 1.0: metachloroperbenzoic acid 2;
(8) allyl group seven phenyl silsesquioxanes that step (7) weighed are dispersed in 50ml methylene dichloride, then add metachloroperbenzoic acid;
(9) by step (8) mixing solutions return stirring 2 days in oil bath under 45 DEG C of conditions, room temperature to be naturally cooled to, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 DEG C of conditions of vacuum, dry 24h, draws head product epoxy group(ing) seven phenyl silsesquioxanes.
embodiment 5:epoxy group(ing) seven phenyl silsesquioxane materials that the present embodiment provides and preparation method thereof, its step and component are all basic identical with one of embodiment 1,2,3,4, and its difference is:
The preparation method of described epoxy group(ing) seven phenyl silsesquioxane materials, it comprises the following steps:
(1) take each raw material by following mol ratio: phenyltrimethoxysila,e 1.0: deionized water 2: sodium hydroxide 2;
(2) phenyltrimethoxysila,e, deionized water, the sodium hydroxide that step (1) are weighed mix in the flask that is equipped with prolong, and add 250ml methyl alcohol dispersing and mixing;
(3) by step (2) mixing solutions, return stirring 10 h in oil bath under 50 DEG C 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 DEG C of conditions of vacuum, dry 24h, draws head product T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates;
(4) by prepared step (3) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates under argon shield, add again following raw material, allyltrichlorosilane, triethylamine, its mol ratio is: T7 sodium salt 1.0: allyltrichlorosilane 2: triethylamine 0.05;
(5) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates that step (4) weighed are dispersed in 250 ml toluene, then add triethylamine, allyltrichlorosilane;
(6) by step (5) mixing solutions, 0
oc ice-water bath condition lower magnetic force stirs 10h, and room temperature to be returned back to continues to react 10h 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 1500ml sherwood oil, separate out white solid, suction filtration, then use petroleum ether 3 times, under 60 DEG C of vacuum conditions, be dried 24h, draw allyl group seven phenyl silsesquioxane materials.
(7) by prepared step (6) allyl group seven phenyl silsesquioxanes under argon shield, add again following raw material, allyl group seven phenyl silsesquioxanes, metachloroperbenzoic acid, its mol ratio is: allyl group seven phenyl silsesquioxanes 1.0: metachloroperbenzoic acid 1.5;
(8) allyl group seven phenyl silsesquioxanes that step (7) weighed are dispersed in 50ml trichloromethane, then add metachloroperbenzoic acid;
(9) by step (8) mixing solutions return stirring 2 days in oil bath under 45 DEG C of conditions, room temperature to be naturally cooled to, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 DEG C of conditions of vacuum, dry 24h, draws head product epoxy group(ing) seven phenyl silsesquioxanes.
embodiment 6:epoxy group(ing) seven phenyl silsesquioxane materials that the present embodiment provides and preparation method thereof, its step and component are all basic identical with one of embodiment 1,2,3,4,5, and its difference is:
The preparation method of described epoxy group(ing) seven phenyl silsesquioxane materials, it comprises the following steps:
(1) take each raw material by following mol ratio: phenyltrimethoxysila,e 1.0: deionized water 2: sodium hydroxide 2;
(2) phenyltrimethoxysila,e, deionized water, the sodium hydroxide that step (1) are weighed mix in the flask that is equipped with prolong, and add 250ml THF dispersing and mixing;
(3) by step (2) mixing solutions, return stirring 5 h in oil bath under 80 DEG C of conditions, room temperature to be naturally cooled to, under magnetic agitation, continue reaction 15h, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 DEG C of conditions of vacuum, dry 24h, draws head product T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates;
(4) by prepared step (3) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates under argon shield, then add following raw material, cyclohexenyl trichlorosilane, pyridine, its mol ratio is: T7 sodium salt 1.0: allyltrichlorosilane 2: pyridine 0.02;
(5) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates that step (4) weighed are dispersed in 250 ml THF, then add pyridine, allyltrichlorosilane;
(6) by step (5) mixing solutions, 0
oc ice-water bath condition lower magnetic force stirs 5h, and 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, again filtrate is added in 2000ml methyl alcohol, separate out white solid, suction filtration, then use methanol wash 3 times, under 60 DEG C of vacuum conditions, be dried 24h, draw cyclohexenyl seven phenyl silsesquioxane materials.
(7) by prepared step (6) allyl group seven phenyl silsesquioxanes under argon shield, add again following raw material, allyl group seven phenyl silsesquioxanes, metachloroperbenzoic acid, its mol ratio is: allyl group seven phenyl silsesquioxanes 1.0: metachloroperbenzoic acid 1.5;
(8) alkylene seven phenyl silsesquioxanes that step (7) weighed are dispersed in 45ml methylene dichloride, then add metachloroperbenzoic acid;
(9) by step (8) mixing solutions return stirring 2 days in oil bath under 40 DEG C of conditions, room temperature to be naturally cooled to, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 DEG C of conditions of vacuum, dry 24h, draws head product hexamethylene epoxy group(ing) seven phenyl silsesquioxanes.
In epoxy group(ing) ethyl seven phenyl silsesquioxane SEM pictures, microscopic appearance is petal-shaped structure as shown in Figure 1; Be illustrated in figure 2 epoxy group(ing) seven phenyl silsesquioxanes
1h NMR figure, can find out that from nuclear magnetic spectrum purity reaches more than 95%.
Claims (10)
1. epoxy group(ing) seven phenyl silsesquioxane materials, is characterized in that, its feed composition by following mol ratio is made: alkylene seven phenyl silsesquioxanes are 1.0:1.2 ~ 2 with the ratio of metachloroperbenzoic acid.
2. epoxy group(ing) seven phenyl silsesquioxane materials according to claim 1, it is characterized in that, described alkylene seven phenyl silsesquioxanes are made up of T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates, alkylene trichlorosilane, the second catalyzer, and its mol ratio is: T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates 1.0: alkylene trichlorosilane the 1.2 ~ 2: second catalyzer 0.01 ~ 0.05; T7 sodium salt is made up of 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. alkylene seven phenyl silsesquioxane materials according to claim 2, is characterized in that, described the first catalyzer is one of sodium hydroxide, potassium hydroxide.
4. alkylene seven phenyl silsesquioxane materials according to claim 2, is characterized in that, described the second catalyzer be triethylamine, Trimethylamine 99, diethylamine, pyridine, DMF one of them.
5. alkene seven phenyl silsesquioxane materials according to claim 2, is characterized in that, described thiazolinyl trichlorosilane be vinyl trichloro silane, allyltrichlorosilane, cyclohexenyl trichlorosilane one of them.
6. a preparation method for epoxy group(ing) seven phenyl silsesquioxane materials, is characterized in that, it comprises the steps:
(1) take each raw material by following mol ratio: phenyltrimethoxysila,e 1.0: deionized water 1.1 ~ 5: the first catalyzer 0.5 ~ 2;
(2) phenyltrimethoxysila,e, deionized water, the first catalyzer that step (1) are weighed mix in the flask that is equipped with prolong, and add 250ml the first solvent dispersion to mix;
(3) by step (2) mixing solutions, return stirring 4 ~ 10 h in oil bath under 50 ~ 80 DEG C 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 DEG C of conditions of vacuum, dry 24h, draws head product T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates;
(4) by prepared step (3) T7 sodium salt seven polyphenylsilsesquioxane three sodium silanolates under argon shield, add again following raw material, alkylene trichlorosilane, the second catalyzer, its mol ratio is: T7 sodium salt 1.0: alkylene trichlorosilane the 1.2 ~ 2: 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, alkylene trichlorosilane;
(6) by step (5) mixing solutions ,-10
oc ~ 10
oc ice-water bath condition lower magnetic force stirs 3h ~ 15h, and 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 DEG C of vacuum conditions, be dried 24h, draw alkylene seven phenyl silsesquioxane materials;
(7) by prepared step (6) alkylene seven phenyl silsesquioxanes under argon shield, add again following raw material, alkylene seven phenyl silsesquioxanes, metachloroperbenzoic acid, its mol ratio is: alkylene seven phenyl silsesquioxanes 1.0: metachloroperbenzoic acid 1.2 ~ 2;
(8) alkylene seven phenyl silsesquioxanes that step (7) weighed are dispersed in 40 ~ 50ml the 4th solvent, then add metachloroperbenzoic acid;
(9) by step (8) mixing solutions return stirring 2 days in oil bath under 40 ~ 45 DEG C of conditions, room temperature to be naturally cooled to, stopped reaction, decompression steams solvent, naturally cool to room temperature, suction filtration draws white powder product, and under 60 DEG C of conditions of vacuum, dry 24h, draws head product epoxy group(ing) seven phenyl silsesquioxanes.
7. the preparation method of epoxy group(ing) 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.
8. the preparation method of epoxy group(ing) 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.
9. the preparation method of epoxy group(ing) 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; Described the second solvent be THF, toluene, benzene, ethers one of them.
10. the preparation method of epoxy group(ing) 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; Described the 4th solvent be methylene dichloride, chloroform, THF one of them.
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