CN104311593A - Synthesis method of mono functional group octa-polysilsesquioxane - Google Patents
Synthesis method of mono functional group octa-polysilsesquioxane Download PDFInfo
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- CN104311593A CN104311593A CN201410460043.8A CN201410460043A CN104311593A CN 104311593 A CN104311593 A CN 104311593A CN 201410460043 A CN201410460043 A CN 201410460043A CN 104311593 A CN104311593 A CN 104311593A
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Abstract
The invention discloses a synthesis method of mono functional group octa-polysilsesquioxane prepared from the following components of T7 sodium hepta-polysilsesquioxane trimethylsilanolate sodium, mono functional group trichlorosilane and a second catalyst in the following molar ratio of 1.0:1.2-2:0.01-0.05, the T7 sodium comprises alkyl triethoxy siloxane, deionized water and a first catalyst with the molar ratio of 1.0:1.1-1.5:0.5-2. The method is simple in technique and short in reaction time, the materials provided by the method has the advantages of god structural singleness of the product, high yield, high purity, good stability and good organic solubility, can be used for thermosetting resin, thermoplastic resin and rubber and other polymer modified prepared high performance nano composite materials, and the method is compact in process, and can be used for large scale industrialized production.
Description
Technical field
The present invention relates to the preparation method of a compounds, especially a class simple function group eight gathers the preparation method of cage modle eight polysilsesquioxane.
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 at about 0.7nm ~ 50nm, be made up of inorganic " core " and organic " shell ", each POSS particle is containing 1-8 organic active functional group, these functional groups can carry out being polymerized, grafting, surface bond or other reactions, be easy to carry out molecular designing, form POSS-polymer materials.POSS has organic and inorganic chemical properties concurrently, is characterized in that it can be dissolved in solvent and resin, thus can guarantees to realize molecularly dispersed structure, can reduce viscosity thus can strengthen loading level simultaneously.Because it also becomes to be integrated with the resin compatible of fusing, thus do not affect its processing fluidity.But time below the fusing point that temperature is down to them, just solidify to form nanostructure immediately and cause enhancement.Then just in time contrary as inorganic nano-particles such as nano imvites, because it can not dissolve, because this reducing 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, make the physical strength of polymer materials, second-order transition temperature (
t g), use temperature and thermal stability be obtained for 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 a solvent.Partial hydrolysis-angle-sealing method is RSiX
3the unfilled corner seven that hydrolytic condensation can generate with three silicone hydroxyl under certain condition gathers POSS, then adds function base silane monomer in the ratio of equivalent, further hydrolytic condensation closed loop, obtains single function base POSS.Functional group's derivatization method utilizes existing substituent POSS, obtains required function base POSS molecule by chemical reaction (oxidation, Si―H addition reaction etc.).At present comparatively ripe about the research of eight function base POSS, but eight function base POSS existing problems in the level of response and consistency of solvability and polymkeric substance, make it in performance not as single function base POSS.Traditional preparation list function base POSS key is that the unfilled corner seven obtained with three silicone hydroxyl gathers POSS(T7), being by the synthesis of top band cap, there is the deficiencies such as processing condition complexity, reaction time is long, the abstraction and purification difficulty of product, productive rate are low in it.
Summary of the invention
A kind of novel single function base eight is the object of the present invention is to provide to gather cage modle eight polysilsesquioxane and synthetic method thereof.In order to achieve the above object: the technical solution used in the present invention for organic trimethoxy siloxane is reacted under organic solvent and catalyst action, wash, recrystallization makes T7 metal-salt, then T7 metal-salt reacts again from the different trichlorosilane containing thiazolinyl under solvent and catalyst action, through washing, extraction, dry, recrystallization, finally obtain white product.
Described organic trialkyl siloxanes is: phenyltrimethoxysila,e, cyclohexyl trimethoxy silane, cyclopentyl-trimethoxy-silane, suberyl Trimethoxy silane, trimethoxysilane one of them;
Described single function base eight polysilsesquioxane synthetic method is divided into two steps, its concrete steps are as follows: (1) is first in the flask being furnished with prolong, at room temperature organic trialkyl siloxanes of 1mol is joined in the mixed solution that formula is deionized water 1.1-5mol, oxyhydroxide 0.5mol, solvent 1000 ml forms, be warming up to return stirring 4-10 h in 50-80 DEG C of oil bath; Be cooled to room temperature, under magnetic agitation, continue reaction 10-25 h; Then stopped reaction, decompression steams solvent, and obtain thick product, steam solvent and carry out mother liquor concentrations, be then cooled to room temperature, suction filtration obtains white powder head product T7 metal-salt seven polysilsesquioxane three sodium silanolate, productive rate control 50-98.3%; Again respectively with the 1-5 thick product of solvent wash doubly that consumption is head product quality, obtain head product through vacuum-drying; (2) under argon shield, seven polyphenylene or seven polycyclic hexyls or seven polycyclic amyl group silsesquioxane three sodium silanolate 10mmol are dispersed in 250 ml THF, add 1.5-2 ml triethylamine; Be placed in ice-water bath, rapidly single function base trichlorosilane 13mmol added wherein under magnetic agitation, in ice-water bath, react 3 h-15h; Be cooled to room temperature and continue stirring 3 h-15h; Add deionized water stopped reaction, separate organic phase, wash three times, dry; Cross and filter siccative, filtrate poured in 1000 ml alcohol, adularescent solid is separated out; Suction filtration, solid alcohol washs three times; The white solid obtained, vacuum-drying obtains product.
In step (1) in T7 reacting metal salt organic solvent used be THF and methyl alcohol, ethanol, Virahol one of them, wherein solvent for use and phenyltrimethoxysila,e volume ratio are 4-28:1, described catalyzer be sodium hydroxide, potassium hydroxide one of them, the amount of substance of phenyltrimethoxysila,e and oxyhydroxide is than being 1:0.50-2.
Phenyltrimethoxysila,e and deionized water amount of substance mol ratio are 1:1.1-5.
In step (2) in reaction solvent for use be THF, toluene, benzene, ethers one of them.
In step (2), in reaction, single function base trichlorosilane used is vinyl trichloro silane, allyltrichlorosilane, trichlorosilane, aminopropyltrichlorosilane, ethene acyloxy trichlorosilane, epoxypropyl trichlorosilane, 3-bromopropyl trichlorosilane, 3-(metacryloxy) propyltrichlorosilan, 3-acryl oxygen base propyltrichlorosilan, 2-methoxycarbonyl ethyl trichlorosilane, 2-acetoxyethyltrichlorosilane, 2-(4-chlorine sulfonyl-phenyl) ethyl trichlorosilane, 7-octyl group-1-alkynes trichlorosilane, 3-cyanopropyl trichlorosilane one of them, 7-octyl group-1-alkynes trichlorosilane one of them, the ratio 1.2-2.0:7 of single function base trichlorosilane and phenyltrimethoxysila,e amount of substance, single function base trichlorosilane and T7 metal-salt are than being 1.2-2:1.
In step (2) in reaction used catalyst be triethylamine, Trimethylamine 99, diethylamine, pyridine, DMF one of them.In step (2) in reaction when crystalline deposit washing solvent used be methyl alcohol, ethanol, isopropyl alcohols, sherwood oil one of them.
Embodiment
Embodiment 1
First in the flask being furnished with prolong, add cyclohexyl trimethoxy silane (50.0 g, 244.7 mmol), sodium hydroxide (5 g, 125 mmol), deionized water (5.5 g, 305.6mmol), THF 250 ml, be warming up to return stirring 5 h in 70 DEG C of oil baths.Be cooled to room temperature, under magnetic agitation, continue reaction 15 h.Then stopped reaction, decompression steams solvent, obtains white powder product T7 metal-salt seven polycyclic hexyl silsesquioxane three sodium silanolate; Product is placed in 60 DEG C of vacuum drying ovens dry 24 hours.Productive rate is about 98.3%.Under argon shield, seven polycyclic hexyl silsesquioxane three sodium silanolates (10.5 g, 10.08 mmol) are dispersed in 250 ml THF, add 1.5 ml triethylamines.Be placed in ice-water bath, rapidly vinyl trichloro silane (2.105 g, 13.05 mmol) added wherein under magnetic agitation, in ice-water bath, react 3 h.Return back to room temperature and continue stirring 3 h.Add deionized water stopped reaction, separate organic phase, wash three times, anhydrous magnesium sulfate drying.Cross and filter siccative, filtrate poured in 1000 ml methyl alcohol, adularescent solid is separated out.Suction filtration, solids with methanol washs three times.The white solid obtained, dry 24h in 60 DEG C of vacuum drying ovens.Productive rate is about 83.9%.
Embodiment 2
First in the flask being furnished with prolong, add phenyltrimethoxysila,e (99 g, 499.2 mmol), sodium hydroxide (10 g, 250mmol), deionized water (11 g, 611.1mmol), THF 250 ml, be warming up to return stirring 6 h in 75 DEG C of oil baths.Be cooled to room temperature, under magnetic agitation, continue reaction 15 h.Then stopped reaction, decompression steams solvent, obtains white powder product T7 metal-salt seven polyphenylsilsesquioxane three sodium silanolate; Product is placed in 60 DEG C of vacuum drying ovens dry 24 hours.Productive rate is about 90.3%.Under argon shield, seven polyphenylsilsesquioxane three sodium silanolates (20.74 g, 20.08 mmol) are dispersed in 500ml THF, add 3 ml triethylamines.Be placed in ice-water bath, rapidly vinyl trichloro silane (4.21g, 26.10 mmol) added wherein under magnetic agitation, in ice-water bath, react 4 h.Return back to room temperature and continue stirring 3 h.Add deionized water stopped reaction, separate organic phase, wash three times, anhydrous magnesium sulfate drying.Cross and filter siccative, filtrate poured in 2000 ml methyl alcohol, adularescent solid is separated out.Suction filtration, solids with methanol washs three times.The white solid obtained, dry 24h in 60 DEG C of vacuum drying ovens.Productive rate is about 81.9%.
Embodiment 3
First in the flask being furnished with prolong, add phenyltrimethoxysila,e (49.5 g, 249.6 mmol), sodium hydroxide (5 g, 125 mmol), deionized water (5.5 g, 305.6mmol), methyl alcohol 250 ml, be warming up to return stirring 5 h in 70 DEG C of oil baths.Be cooled to room temperature, under magnetic agitation, continue reaction 15 h.Then stopped reaction, decompression steams partial solvent, and cooling, filtration, washing obtain white powder product T7 metal-salt seven polyphenylsilsesquioxane three sodium silanolate; Product is placed in 60 DEG C of vacuum drying ovens dry 24 hours.Productive rate is about 87%.Under argon shield, seven polyphenylsilsesquioxane three sodium silanolates (10.037 g, 10.04 mmol) are dispersed in 250 ml toluene, add 1.5 ml Trimethylamine 99s.Be placed in ice-water bath, rapidly trichlorosilane (2.105 g, 13.05 mmol) added wherein under magnetic agitation, in ice-water bath, react 3 h.Return back to room temperature and continue stirring 3 h.Add deionized water stopped reaction, separate organic phase, wash three times, anhydrous magnesium sulfate drying.Cross and filter siccative, filtrate poured in 1000 ml methyl alcohol, adularescent solid is separated out.Suction filtration, solids with methanol washs three times.The white solid obtained, dry 24h in 60 DEG C of vacuum drying ovens.Productive rate is about 84%.
Embodiment 4
First in the flask being furnished with prolong, add phenyltrimethoxysila,e (49.5 g, 249.6 mmol), sodium hydroxide (5 g, 125 mmol), deionized water (5.5 g, 305.6mmol), THF 250 ml, be warming up to return stirring 5 h in 70 DEG C of oil baths.Be cooled to room temperature, under magnetic agitation, continue reaction 15 h.Then stopped reaction, decompression steams solvent, obtains white powder product T7 metal-salt seven polyphenylsilsesquioxane three sodium silanolate; Product is placed in 60 DEG C of vacuum drying ovens dry 24 hours.Productive rate is about 98.3%.Under argon shield, seven polyphenylsilsesquioxane three sodium silanolates (10.037 g, 10.04 mmol) are dispersed in 250 ml THF, add 1.5 ml triethylamines.Be placed in ice-water bath, rapidly allyltrichlorosilane (2.290 g, 13.05 mmol) added wherein under magnetic agitation, in ice-water bath, react 3 h.Return back to room temperature and continue stirring 3 h.Add deionized water stopped reaction, separate organic phase, wash three times, anhydrous magnesium sulfate drying.Cross and filter siccative, filtrate poured in 1000 ml methyl alcohol, adularescent solid is separated out.Suction filtration, solids with methanol washs three times.The white solid obtained, dry 24h in 60 DEG C of vacuum drying ovens.Productive rate is about 89.8%.
Claims (7)
1. the synthetic method of single function base eight polysilsesquioxane, it is characterized in that organic trialkyl siloxanes reacts under organic solvent and catalyst action, wash, recrystallization makes T7 metal-salt seven polysilsesquioxane three sodium silanolate, then T7 metal-salt reacts under solvent and catalyst action with the trichlorosilane containing functional group again, through washing, extraction, dry, recrystallization, finally obtain white product list function base eight polysilsesquioxane;
Described organic trialkyl siloxanes is: phenyltrimethoxysila,e, cyclohexyl trimethoxy silane, cyclopentyl-trimethoxy-silane, suberyl Trimethoxy silane, trimethoxysilane one of them;
Described single function base eight polysilsesquioxane synthetic method is divided into two steps, its concrete steps are as follows: (1) is first in the flask being furnished with prolong, at room temperature organic trialkyl siloxanes of 1mol is joined in the mixed solution that formula is deionized water 1.1-5mol, oxyhydroxide 0.5mol, solvent 1000 ml forms, be warming up to return stirring 4-10 h in 50-80 DEG C of oil bath; Be cooled to room temperature, under magnetic agitation, continue reaction 10-25 h; Then stopped reaction, decompression steams solvent, and obtain thick product, steam solvent and carry out mother liquor concentrations, be then cooled to room temperature, suction filtration obtains white powder head product T7 metal-salt seven polysilsesquioxane three sodium silanolate, productive rate control 50-98.3%; Again respectively with the 1-5 thick product of solvent wash doubly that consumption is head product quality, obtain head product through vacuum-drying; (2) under argon shield, seven polyphenylene or seven polycyclic hexyls or seven polycyclic amyl group silsesquioxane three sodium silanolate 10mmol are dispersed in 250 ml THF, add 1.5-2 ml triethylamine; Be placed in ice-water bath, rapidly single function base trichlorosilane 13mmol added wherein under magnetic agitation, in ice-water bath, react 3 h-15h; Be cooled to room temperature and continue stirring 3 h-15h; Add deionized water stopped reaction, separate organic phase, wash three times, dry; Cross and filter siccative, filtrate poured in 1000 ml alcohol, adularescent solid is separated out; Suction filtration, solid alcohol washs three times; The white solid obtained, vacuum-drying obtains product.
2. method according to claim 1, to it is characterized in that in step (1) in T7 reacting metal salt organic solvent used be THF and methyl alcohol, ethanol, Virahol one of them, wherein solvent for use and phenyltrimethoxysila,e volume ratio are 4-28:1, described catalyzer be sodium hydroxide, potassium hydroxide one of them, the amount of substance of phenyltrimethoxysila,e and oxyhydroxide is than being 1:0.50-2.
3. method according to claim 1, is characterized in that phenyltrimethoxysila,e and deionized water amount of substance mol ratio are 1:1.1-5.
4. method according to claim 1, to it is characterized in that in step (2) in reaction solvent for use be THF, toluene, benzene, ethers one of them.
5. method according to claim 1, it is characterized in that in step (2), in reaction, single function base trichlorosilane used is vinyl trichloro silane, allyltrichlorosilane, trichlorosilane, aminopropyltrichlorosilane, ethene acyloxy trichlorosilane, epoxypropyl trichlorosilane, 3-bromopropyl trichlorosilane, 3-(metacryloxy) propyltrichlorosilan, 3-acryl oxygen base propyltrichlorosilan, 2-methoxycarbonyl ethyl trichlorosilane, 2-acetoxyethyltrichlorosilane, 2-(4-chlorine sulfonyl-phenyl) ethyl trichlorosilane, 7-octyl group-1-alkynes trichlorosilane, 3-cyanopropyl trichlorosilane one of them, 7-octyl group-1-alkynes trichlorosilane one of them, the ratio 1.2-2.0:7 of single function base trichlorosilane and phenyltrimethoxysila,e amount of substance, single function base trichlorosilane and T7 metal-salt are than being 1.2-2:1.
6. method according to claim 1, to it is characterized in that in step (2) in reaction used catalyst be triethylamine, Trimethylamine 99, diethylamine, pyridine, DMF one of them.
7. method according to claim 1, to it is characterized in that in step (2) in reaction when crystalline deposit washing solvent used be methyl alcohol, ethanol, isopropyl alcohols, sherwood oil one of them.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992347A (en) * | 2014-05-06 | 2014-08-20 | 上海大学 | Epoxy heptaphenyl silsesquioxane material and preparation method thereof |
| CN108976423A (en) * | 2018-06-11 | 2018-12-11 | 中国科学院上海有机化学研究所 | A kind of cage-type silsesquioxane of cyano-containing and preparation method thereof |
| CN109053795A (en) * | 2018-08-15 | 2018-12-21 | 哈尔滨工业大学 | A kind of preparation method of more methacryloxy sesquialter silane |
| CN112175304A (en) * | 2020-10-20 | 2021-01-05 | 西北工业大学 | POSS (polyhedral oligomeric silsesquioxane) modified ethylene propylene diene monomer composite material with reaction type cage-type silsesquioxane structure and preparation method thereof |
| CN114685795A (en) * | 2020-12-28 | 2022-07-01 | 广州一新科技有限公司 | Cage type polysilsesquioxane and preparation method thereof |
-
2014
- 2014-09-11 CN CN201410460043.8A patent/CN104311593A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992347A (en) * | 2014-05-06 | 2014-08-20 | 上海大学 | Epoxy heptaphenyl silsesquioxane material and preparation method thereof |
| CN108976423A (en) * | 2018-06-11 | 2018-12-11 | 中国科学院上海有机化学研究所 | A kind of cage-type silsesquioxane of cyano-containing and preparation method thereof |
| CN109053795A (en) * | 2018-08-15 | 2018-12-21 | 哈尔滨工业大学 | A kind of preparation method of more methacryloxy sesquialter silane |
| CN112175304A (en) * | 2020-10-20 | 2021-01-05 | 西北工业大学 | POSS (polyhedral oligomeric silsesquioxane) modified ethylene propylene diene monomer composite material with reaction type cage-type silsesquioxane structure and preparation method thereof |
| CN114685795A (en) * | 2020-12-28 | 2022-07-01 | 广州一新科技有限公司 | Cage type polysilsesquioxane and preparation method thereof |
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Application publication date: 20150128 |