CN104610341A - Simple function group octamer-cage type silsesquioxane preparation method - Google Patents
Simple function group octamer-cage type silsesquioxane preparation method Download PDFInfo
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Abstract
The invention discloses a simple function group octamer-cage type silsesquioxane preparation method, during preparation, dibutyltindilaurate as a catalyst is mixed with hepta trisilanol, amino silane and an organic solvent for reaction for preparation, by synergistic catalytic effect of the catalyst and ammonia compounds, side reaction can be effectively reduced, and the yield of the target product can be improved. Compared with a traditional simple function group polyhedral oligomeric silsesquioxane (POSS) preparation method, the simple function group octamer-cage type silsesquioxane preparation method has the characteristics of simple process, easy operation and high yield (most amino POSS yield is more than 50%), quick reaction (within 24 hours), a convenient simple function group POSS preparation method is provided, at the same time various new amino POSS compounds are also provided, and the simple function group octamer-cage type silsesquioxane preparation method has very important application value.
Description
Technical field
The invention belongs to the synthesis technical field of silicone oligomer, relate to the preparation method of cage-type silsesquioxane, be specifically related to the preparation method that a kind of simple function group eight gathers cage-type silsesquioxane.
Background technology
Cage-type silsesquioxane is the oligosiloxane of a class nanoscale cagelike structure, and be commonly called as cube silane and ball-type siloxanes etc., its English full name is: Polyhedral Oligomeric Silsesquioxane, referred to as POSS.POSS is a kind of inorganic/organic nano hybrid material with nucleocapsid structure inherently, its structure is shown below, it has regular three-dimensional arrangement, nano-scale, excellent consistency and modifiability, make it in a lot of fields, such as: organometallic catalytic, photoengraving and coating etc., unique effect is all played.
According to the difference of POSS structure type, POSS is mainly divided into three major types: complete same POSS, simple function group POSS, seven poly-POSS.Wherein, simple function group POSS is because of containing active function groups, and there is certain anisotropy, both cage structure can be grafted in main polymer chain as side chain by chemical reaction, the organic/inorganic nano-hybrid materials of processability excellence, electrostatic force and many base materials can be utilized again to carry out compound, obtain the material of property.
At present, the preparation of simple function group POSS mainly adopts three kinds of methods: cohydrolysis condensation method, functional group's derivatization method and unfilled corner closed loop method.Wherein, cohydrolysis condensation method is difficult to obtain the single target product of component, and functional group's derivatization method is only applicable to containing same the replacements POSS of reactive hydrogen atom in R base, the two drawbacks limit their development and the application in monofunctional POSS synthesis field thereof; By comparison, unfilled corner closed loop rule is simple to operate, purification is convenient, applied widely, thus becomes the main method preparing simple function group POSS.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method that a kind of simple function group eight gathers cage-type silsesquioxane, have simple to operate, productive rate is high, swift feature.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of simple function group eight gathers the preparation method of cage-type silsesquioxane, it is characterized in that step is:
1) seven poly-three silanols are first prepared;
2) get poly-three silanols of 0.01 ~ 0.02mol seven to be dissolved in 8 ~ 20mL organic solvent and to be mixed with mixing solutions, be cooled to-7 ~-9 DEG C, 0.005 ~ 0.02mol aminosilane and 2 ~ 10 catalyst drops are added in above-mentioned mixing solutions, reaction 12-24h; Wherein organic solvent is tetrahydrofuran (THF), ethanol or toluene;
3) when organic solvent be tetrahydrofuran (THF) or ethanol time, reaction terminate final vacuum slough organic solvent, with methyl alcohol or acetonitrile wash, can target product be prepared; When organic solvent is toluene, after reaction terminates, reaction soln is poured in methyl alcohol and stirs 1.5-2.5h, separate out precipitation, filter, with methyl alcohol or acetonitrile wash, can target product be prepared.
As improvement, the preparation process of described seven poly-three silanols is:
A, first deionized water 0.11 ~ 0.14mol, solvent 50 ~ 200mL and catalyzer 0.04 ~ 0.07mol mixing and stirring are made into mixing solutions, silane 0.09 ~ 0.11mol is dripped in mixing solutions, after dropwising, back flow reaction 5-24h, wherein catalyzer is sodium hydroxide, lithium hydroxide, tetraethyl ammonium hydroxide or tetramethyl-oxyammonia;
After b, reaction terminate, the organic solvent of vacuum removing at normal temperatures, obtains thick product, then washes with water respectively or methyl alcohol or acetonitrile wash, prepares seven poly-three silicon alkoxides through vacuum-drying; Or directly acid neutralization, the drier preparation seven of washing gathers three silanols after filtration.
Silane in described step a) is ethyl trimethoxy silane, ethyl triethoxysilane, trimethoxysilane, isobutyl triethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, trifluoro propyl Trimethoxy silane, trifluoro propyl triethoxyl silane, cyclohexyl trimethoxy silane, cyclohexyltriethyloxysilane, cyclopentyl-trimethoxy-silane or cyclopentyl triethoxyl silane.
Solvent in described step a) is tetrahydrofuran (THF), Virahol, acetone/methanol mixed solvent, acetone/ethanol mixed solvent, acetone/isopropanol mixed solvent, acetonitrile/alcohol mixed solvent or acetonitrile/methanol mixed solvent, and wherein in mixed solvent, ketone, nitrile solvents are 4 ~ 7:1 with the ratio of the volume of alcoholic solvent.
When catalyzer in described step a) is sodium hydroxide, tetraethyl ammonium hydroxide or tetramethyl-oxyammonia, reflux time is 5-10h; When catalyzer is lithium hydroxide, reflux time is 18-24h.
In described step b), the acid of acid neutralization is hydrochloric acid or acetic acid, and the concentration of hydrochloric acid or acetic acid is 1mol/L, and washing drying refers to washing or methyl alcohol or acetonitrile wash, in atmosphere dry 6 ~ 8 days.
As preferably, described aminosilane is aminopropyl trimethoxysilane, normal-butyl aminopropyl trimethoxysilane, aminoethylaminopropyl Trimethoxy silane or two (3-trimethoxy-silylpropyl) amine.
As preferably, described catalyzer is the positive fourth tin of tin dilaurate two.
As improvement, described methyl alcohol, acetonitrile or n-hexane refer to methyl alcohol, acetonitrile or n-hexane twice.
In addition, be obtain high purity product, partial target product also needs methylene dichloride again to dissolve and the purification step such as recrystallization.
Compared with prior art, the invention has the advantages that: with seven poly-three silanols and aminosilane for raw material, adopt the mode that low temperature feeds intake, adopt di-n-butyltin dilaurate to be catalyzer simultaneously, prepared the amino POSS of multiple simple function group efficiently.Wherein, the amino POSS of many simple function groups is new compound.Therefore, the present invention provide a kind of prepare simple function group POSS method easily while also provide many novel amino POSS compounds with very important using value; In addition, compared with traditional method preparing simple function group POSS, present invention process is simple to operation, productive rate is high (most of amino POSS productive rate is more than 50%), reaction fast (within 24h), has very important using value.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart that simple function group eight provided by the invention gathers cage-type silsesquioxane.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
The preparation (R=i-Bu) of poly-isobutyl-three silanol of embodiment one: seven
100mL tetrahydrofuran (THF), 1.80g (0.045mol) sodium hydroxide, secondary deionized water 2.40g is added in the 500mL there-necked flask that prolong, agitator are housed, after stirring, slow dropping isobutyl triethoxy silane (23.14g, 0.105mol), then backflow is heated to, reaction 10h.Be cooled to room temperature final vacuum and slough THF, add 100mL dissolve with methanol.After abundant dissolving, add 100mL acetic acid (1mol/L) neutralization, suction filtration, washing twice, acetonitrile wash twice.Air drying 7 days, obtains 12.38g white powdery solids, and productive rate is 95.8%.
The preparation (R=Ph) of embodiment two: seven polyphenylene three silanol
135mL acetone, 25mL Virahol, 2.12g (0.05mol) hydronium(ion) Lithium Oxide 98min and deionized water 1.42g is added in the 250mL there-necked flask that prolong, agitator are housed, be heated to backflow, slowly drip phenyl triethoxysilane (24.60g at reflux, 0.10mol), 24h is reacted.Add the HCl neutralization of 90mL (1mol/L), stir 2h, suction filtration, wash 6 times, air drying 7 days, obtains 14.8g white powdery solids, and productive rate is 98.1%.
Embodiment three: normal-butyl aminopropyl seven gather isobutyl-POSS preparation (R '=CH
2cH
2cH
2cH
3)
Seven poly-isobutyl-three silanol (7.90g are added in 100mL round-bottomed flask, 0.01mol) and THF10mL, be cooled to-8 DEG C, add normal-butyl aminopropyl trimethoxysilane (2.35g, 0.01mol) and two di-n-butyltin dilaurates, reaction 16h; Vacuum sloughs THF, acetonitrile wash twice, obtains 8.30g white solid after vacuum-drying, and productive rate is 81.2%.
Embodiment four: the preparation of normal-butyl aminopropyl seven polyphenylene POSS (R '=CH
2cH
2cH
2cH
3)
Seven polyphenylene three silanol (9.30g are added in 100mL round-bottomed flask, 0.01mol) with toluene 12mL, be cooled to-8 DEG C, drip normal-butyl aminopropyl trimethoxysilane (2.35g, 0.01mol) and two di-n-butyltin dilaurates, reaction 12h; Solution pours in 250mL methyl alcohol and stirs 2h, and filter after leaving standstill, gained solid is dissolved in methylene dichloride again, and filter, vacuum sloughs methylene dichloride, acetonitrile wash twice, obtains 7.02g white solid after vacuum-drying, and productive rate is 60.4%.
Embodiment five: the preparation (R=i-Bu) of the amino POSS of bridge-type
Seven poly-isobutyl-three silanol (7.90g are added in 100mL round-bottomed flask, 0.01mol) and THF10mL, be cooled to-8 DEG C, add two (3-trimethoxy-silylpropyl) amine (1.71g, 0.005mol) and two di-n-butyltin dilaurates.After reaction 18h, vacuum sloughs THF, methanol wash twice, acetonitrile wash twice, filters, obtains a large amount of white solid; Again be dissolved into toluene-acetonitrile mixed system, recrystallization, obtain 4.90g white solid after vacuum-drying, productive rate 51.1%.
Embodiment six: the preparation (R=Ph) of the amino POSS of bridge-type
Seven polyphenylene three silanol (9.30g are added in 100mL round-bottomed flask, 0.01mol) with toluene 15mL, be cooled to-8 DEG C, add two (3-trimethoxy-silylpropyl) amine (1.71g, 0.005mol) and two di-n-butyltin dilaurates; After reaction 12h, solution pours in 250mL methyl alcohol and stirs 2h, and standing postprecipitation goes out a large amount of white solid; Filter, methyl alcohol, acetonitrile wash twice, toluene-acetonitrile recrystallization, obtain white solid 2.75g after vacuum-drying, productive rate 24.8%.
Claims (10)
1. simple function group eight gathers a preparation method for cage-type silsesquioxane, it is characterized in that step is:
1) seven poly-three silanols are first prepared;
2) get poly-three silanols of 0.01 ~ 0.02mol seven to be dissolved in 8 ~ 20mL organic solvent and to be mixed with mixing solutions, be cooled to-7 ~-9 DEG C, 0.005 ~ 0.02mol aminosilane and 2 ~ 10 catalyst drops are added in above-mentioned mixing solutions, reaction 12-24h; Wherein organic solvent is tetrahydrofuran (THF), ethanol or toluene;
3) when organic solvent be tetrahydrofuran (THF) or ethanol time, reaction terminate final vacuum slough organic solvent, with methyl alcohol or acetonitrile wash, can target product be prepared; When organic solvent is toluene, after reaction terminates, reaction soln is poured in methyl alcohol and stirs 1.5-2.5h, separate out precipitation, filter, with methyl alcohol or acetonitrile wash, can target product be prepared.
2. preparation method according to claim 1, is characterized in that the preparation process of described seven poly-three silanols is:
A, first deionized water 0.11 ~ 0.14mol, solvent 50 ~ 200mL and catalyzer 0.04 ~ 0.07mol mixing and stirring are made into mixing solutions, silane 0.09 ~ 0.11mol is dripped in mixing solutions, after dropwising, back flow reaction 5-24h, wherein catalyzer is sodium hydroxide, lithium hydroxide, tetraethyl ammonium hydroxide or tetramethyl-oxyammonia;
After b, reaction terminate, the organic solvent of vacuum removing at normal temperatures, obtains thick product, then washes with water respectively or methyl alcohol or acetonitrile wash, prepares seven poly-three silicon alkoxides through vacuum-drying; Or directly acid neutralization, the drier preparation seven of washing gathers three silanols after filtration.
3. preparation method according to claim 2, is characterized in that: the silane in described step a) is ethyl trimethoxy silane, ethyl triethoxysilane, trimethoxysilane, isobutyl triethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, trifluoro propyl Trimethoxy silane, trifluoro propyl triethoxyl silane, cyclohexyl trimethoxy silane, cyclohexyltriethyloxysilane, cyclopentyl-trimethoxy-silane or cyclopentyl triethoxyl silane.
4. preparation method according to claim 2, it is characterized in that: the solvent in described step a) is tetrahydrofuran (THF), Virahol, acetone/methanol mixed solvent, acetone/ethanol mixed solvent, acetone/isopropanol mixed solvent, acetonitrile/alcohol mixed solvent or acetonitrile/methanol mixed solvent, wherein in mixed solvent, ketone, nitrile solvents are 4 ~ 7:1 with the ratio of the volume of alcoholic solvent.
5. preparation method according to claim 2, is characterized in that: when the catalyzer in described step a) is sodium hydroxide, tetraethyl ammonium hydroxide or tetramethyl-oxyammonia, and reflux time is 5-10h; When catalyzer is lithium hydroxide, reflux time is 18-24h.
6. preparation method according to claim 2, it is characterized in that: in described step b), the acid of acid neutralization is hydrochloric acid or acetic acid, the concentration of hydrochloric acid or acetic acid is 1mol/L, and washing drying refers to washing or methyl alcohol or acetonitrile wash, in atmosphere dry 6 ~ 8 days or vacuum-drying 24h.
7. preparation method according to claim 1, is characterized in that: described aminosilane is aminopropyl trimethoxysilane, normal-butyl aminopropyl trimethoxysilane, aminoethylaminopropyl Trimethoxy silane or two (3-trimethoxy-silylpropyl) amine.
8. preparation method according to claim 1, is characterized in that: described catalyzer is the positive fourth tin of tin dilaurate two.
9. preparation method according to claim 1, is characterized in that: described methyl alcohol, acetonitrile or n-hexane refer to methyl alcohol, acetonitrile or n-hexane twice.
10. preparation method according to claim 1, is characterized in that: described target product also can dissolve and recrystallization purification step by methylene dichloride again, to obtain the higher product of purity.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866969A (en) * | 2017-01-17 | 2017-06-20 | 北京理工大学 | A kind of preparation method of incomplete condensation phenylsilsesquioxane lithium salts |
| CN110511381A (en) * | 2019-09-10 | 2019-11-29 | 哈尔滨工业大学 | A kind of synthetic method of seven isobutyl groups, three silicone hydroxyl POSS |
| CN111255183A (en) * | 2020-01-17 | 2020-06-09 | 江西省昭昀建设工程有限公司 | Novel building material and outer wall construction method thereof |
| CN111268945A (en) * | 2020-01-17 | 2020-06-12 | 江西省昭昀建设工程有限公司 | Environment-friendly building exterior wall material and construction method thereof |
-
2013
- 2013-11-04 CN CN201310537932.5A patent/CN104610341A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 胡建坤: "笼型倍半硅氧烷的制备、表征及其在水性聚氨酯中的应用研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866969A (en) * | 2017-01-17 | 2017-06-20 | 北京理工大学 | A kind of preparation method of incomplete condensation phenylsilsesquioxane lithium salts |
| CN110511381A (en) * | 2019-09-10 | 2019-11-29 | 哈尔滨工业大学 | A kind of synthetic method of seven isobutyl groups, three silicone hydroxyl POSS |
| CN111255183A (en) * | 2020-01-17 | 2020-06-09 | 江西省昭昀建设工程有限公司 | Novel building material and outer wall construction method thereof |
| CN111268945A (en) * | 2020-01-17 | 2020-06-12 | 江西省昭昀建设工程有限公司 | Environment-friendly building exterior wall material and construction method thereof |
| CN111255183B (en) * | 2020-01-17 | 2021-06-08 | 江西省昭昀建设工程有限公司 | Novel building material and outer wall construction method thereof |
| CN111268945B (en) * | 2020-01-17 | 2021-11-09 | 江西省昭昀建设工程有限公司 | Environment-friendly building exterior wall material and construction method thereof |
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