CN110483779A - A kind of synthetic method of more aminopropyl cage type polysilsesquioxanes - Google Patents
A kind of synthetic method of more aminopropyl cage type polysilsesquioxanes Download PDFInfo
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- CN110483779A CN110483779A CN201910854382.7A CN201910854382A CN110483779A CN 110483779 A CN110483779 A CN 110483779A CN 201910854382 A CN201910854382 A CN 201910854382A CN 110483779 A CN110483779 A CN 110483779A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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Abstract
A kind of synthetic method of more aminopropyl cage type polysilsesquioxanes, belongs to POSS preparation technical field.The method is as follows: aminopropyl front three/Ethoxysilane is instilled in methanol solution；Hydrochloric acid is instilled in methanol and aminopropyl front three/Ethoxysilane mixed solution, in 40~50 DEG C of 24~36h of hydrolysis-condensation reaction, obtains clear solution；The clear solution that step 2 is obtained carries out concentrated by rotary evaporation, and ethyl alcohol is added and is precipitated, and filters i.e. much aminopropyl cage type polysilsesquioxane.Advantages of the present invention are as follows: the present invention uses the etoh solvent with high polarity of economic green in last handling process.Synthesize safety with low temperature, post-processing approach pollution is small, and treatment conditions are mild, and product purity is high, and yield is high, and product is in stable condition is in granular form, it is economical easy to handle the advantages that.
Description
Technical field
The invention belongs to POSS preparation technical fields, and in particular to a kind of synthesis of more aminopropyl cage type polysilsesquioxanes
Method.
Background technique
Polyhedral polysilsesquioxane (Polyhedral Oligomeric Silsesquioxane, abbreviation POSS) is one
Class has the organic-inorganic compound of special skeleton, and general structure is (SiO1.5R) n (n=6.8.10.12), it can be common that T8
Cagelike structure.Cage modle skeleton composed by the-Si-O-Si- as made of its internal Si atom and O atom alternating and outside can be set
The presence (R can be active group or inertia group) for counting group R makes POSS have both good thermal stability, dielectric properties and anti-
Answer controllability.Simultaneously as own molecular scale only solves tradition in nanoscale and itself excellent compatibility, POSS
Nano material problem easy to reunite, has in terms of the modifying and decorating of material and has great advantage.Currently, POSS is in such as dielectric material
There is applications well in many fields such as material, aerospace, molecular self-assembling.
Currently, existing more aminopropyl POSS synthetic methods, mostly with methanol as solvent, 90 DEG C of pyroreactions, due to methanol
Boiling point at 64.7 DEG C, 90 DEG C of reactions can generate a large amount of steam, for largely synthesizing the experimental provision requirement of more aminopropyl POSS
It is very high, and the more aminopropyl POSS of existing synthetic method need to be precipitated out with THF, THF is 2B class carcinogenic substance, is had in body
Evil, and by THF treated more aminopropyl POSS states mostly at hard bulk, it is not easy to the product for grinding, and preparing
Purity is low, state labile.
Summary of the invention
More aminopropyl POSS are post-processed using tetrahydrofuran the purpose of the present invention is to solve existing, product
Purity is low, state labile, general agglutination, is in high hard state block structure after dry, not easy grinding, and THF consuming is big, to people
The problems such as body is harmful, and dangerous using methanol as solvent pyroreaction, provides a kind of more aminopropyl cage type polysilsesquioxanes
Synthetic method.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of synthetic method of more aminopropyl cage type polysilsesquioxanes, the method comprises the following steps:
Step 1: aminopropyl front three/Ethoxysilane is instilled in methanol solution；
Step 2: hydrochloric acid is instilled in methanol and aminopropyl front three/Ethoxysilane mixed solution, in 40~50 DEG C of water
24~36h of condensation reaction is solved, clear solution is obtained；
Step 3: the clear solution that step 2 is obtained carries out concentrated by rotary evaporation, and ethyl alcohol is added and is precipitated, and filters i.e. much
Aminopropyl cage type polysilsesquioxane.
The present invention having the beneficial effect that compared with the existing technology
1,40~50 DEG C of low-temp reactions, product iodine are highly-safe.64.7 DEG C of methanol boiling point, existing synthetic method
In 90 DEG C of pyroreactions, iodine can generate a large amount of steam, be condensed back to experiment and require relatively high, laboratory is not easy reality
It tests.40~50 DEG C of low-temp reactions of the invention have very big advantage for laboratory amplification production.
2, the present invention uses the etoh solvent with high polarity of economic green in last handling process.Have
Low temperature synthesis safety, post-processing approach pollution is small, and treatment conditions are mild, and product purity is high, and yield is high, and product is in stable condition is in
The advantages that graininess, economy is easy to handle.
3, by the present invention in that with the solvent (ethyl alcohol) of green economy, precipitation process is carried out to more aminopropyl POSS, and logical
The mixed solution for crossing ethyl alcohol repeatedly purifies more aminopropyl POSS, obtains more aminopropyl POSS of high yield high-purity.
4, the synthetic method of the more aminopropyl POSS of the present invention only need to be and more in 40~50 DEG C of 24~36h of low-temp reaction
Aminopropyl POSS is come out with ethanol precipitation, and harm to the human body is small, environmentally friendly, and treated more aminopropyl POSS product shapes
State is stablized, white powdered.
Detailed description of the invention
Fig. 1 is the mass spectrogram that more aminopropyl POSS are synthesized with alcohol treatment；
Fig. 2 is the infrared figure that more aminopropyl POSS are synthesized with alcohol treatment.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawings and examples, and however, it is not limited to this,
All to be modified to technical solution of the present invention or equivalent replacement, range without departing from the spirit of the technical scheme of the invention should all
Cover within the protection scope of the present invention.
Specific embodiment 1: present embodiment record be a kind of more aminopropyl cage type polysilsesquioxanes synthesis side
Method, the method comprises the following steps:
Step 1: aminopropyl front three/Ethoxysilane is instilled in methanol solution；"/" indicates "or"；
Step 2: hydrochloric acid is instilled in methanol and aminopropyl front three/Ethoxysilane mixed solution, in 40~50 DEG C of water
24~36h of condensation reaction is solved, clear solution is obtained；
Step 3: the clear solution that step 2 is obtained carries out concentrated by rotary evaporation, and ethyl alcohol is added and is precipitated, and filters i.e. much
Aminopropyl cage type polysilsesquioxane (white powder).
Specific embodiment 2: a kind of synthesis of more aminopropyl cage type polysilsesquioxanes described in specific embodiment one
Method, in step 1, the volume ratio of the aminopropyl front three/Ethoxysilane and methanol solution is 12:1.The methanol solution
It is pure to analyze.
Specific embodiment 3: a kind of synthesis of more aminopropyl cage type polysilsesquioxanes described in specific embodiment one
Method, in step 1, the rate of addition of the aminopropyl front three/Ethoxysilane is controlled in 20 drops/min.
Specific embodiment 4: a kind of synthesis of more aminopropyl cage type polysilsesquioxanes described in specific embodiment one
Method, in step 2, the concentration of the hydrochloric acid is 10vol.%~37vol.%.
Specific embodiment 5: a kind of synthesis of more aminopropyl cage type polysilsesquioxanes described in specific embodiment one
Method, in step 2, the volume ratio of the hydrochloric acid and methanol and aminopropyl front three/Ethoxysilane mixed solution is 2:13.
Specific embodiment 6: a kind of synthesis of more aminopropyl cage type polysilsesquioxanes described in specific embodiment one
Method, in step 3, the temperature of the concentrated by rotary evaporation is 40~60 DEG C, and the volume after concentration is the 1/4~1/2 of original volume.
Specific embodiment 7: a kind of synthesis of more aminopropyl cage type polysilsesquioxanes described in specific embodiment one
Method, in step 3, the volume ratio of more aminopropyl POSS and ethyl alcohol in the clear solution are 1:1 or 1:2.
Specific embodiment 8: a kind of more aminopropyl cages described in any specific embodiment of specific embodiment one to seven
The synthetic method of type polysilsesquioxane, further includes step 4: being dissolved more aminopropyl POSS using methanol, more ammonia third after dissolution
Concentration of the base POSS in mixed solution is 0.1g/ml, is then rotated to the 1/4~1/2 of original volume, and ethyl alcohol is added and is sunk
It forms sediment, the volume ratio of more aminopropyl POSS and ethyl alcohol is 1:1 or 1:2, repeats 3~5 times to get the more ammonia of purity >=70wt.% are arrived
Propyl POSS.Described repetition 3~5 times refer to that ethyl alcohol, which is added, repeatedly to be precipitated.
Embodiment 1:
A kind of synthetic method of more aminopropyl cage type polysilsesquioxanes, the method comprises the following steps:
Step 1: aminopropyl front three/Ethoxysilane is instilled in methanol solution；Aminopropyl front three/ethyoxyl the silicon
The volume ratio of alkane and methanol solution is 12:1；The methanol solution is that analysis is pure；The drop of the aminopropyl front three/Ethoxysilane
Acceleration Control is in 20 drops/min；
Step 2: hydrochloric acid is instilled in methanol and aminopropyl front three/Ethoxysilane mixed solution, is contracted in 40 DEG C of hydrolysis
It closes reaction for 24 hours, obtains clear solution；The concentration of the hydrochloric acid is 10vol.%；The hydrochloric acid and methanol and aminopropyl front three/second
The volume ratio of the mixed solution of oxysilane is 2:13；
Step 3: the clear solution that step 2 is obtained carries out concentrated by rotary evaporation, and ethyl alcohol is added and is precipitated, and filters i.e. much
Aminopropyl cage type polysilsesquioxane (white powder).The temperature of the concentrated by rotary evaporation is 50 DEG C, and the volume after concentration is substance
Long-pending 1/4.The volume ratio of more aminopropyl POSS and ethyl alcohol in the clear solution are 1:1.
Step 4: more aminopropyl POSS are dissolved using methanol, more aminopropyl POSS are dense in mixed solution after dissolution
Degree is 0.1g/ml, is then rotated to the 1/4 of original volume, and ethyl alcohol is added and is precipitated, the volume ratio of more aminopropyl POSS and ethyl alcohol
For 1:1, it is repeated 4 times to get the more aminopropyl POSS of purity >=70wt.% are arrived.Fig. 1 is to synthesize more aminopropyls with alcohol treatment
The mass spectrogram of POSS；M/z is that 881.4-884.8 is [more aminopropyl POSS+H]+Peak and its isotopic peak；M/z is 904.7 to be
[more aminopropyl POSS+Na]+Peak, mass spectrogram proof synthesized more aminopropyl POSS；Fig. 2 is to synthesize more ammonia third with alcohol treatment
The infrared figure of base POSS；3450cm-1For-NH2Stretching vibration peak, 1580cm-1For-NH2Face in stretching vibration peak, 680cm-1
For-NH2Face external extension vibration peak；2980,2870cm-1For-CH2Stretching vibration peak；1100cm-1For the flexible of-Si-O-Si
Vibration peak is the cage modle framework characteristic peak of more aminopropyl POSS.
Claims (8)
1. a kind of synthetic method of more aminopropyl cage type polysilsesquioxanes, it is characterised in that: the method comprises the following steps:
Step 1: aminopropyl front three/Ethoxysilane is instilled in methanol solution；
Step 2: hydrochloric acid is instilled in methanol and aminopropyl front three/Ethoxysilane mixed solution, is contracted in 40~50 DEG C of hydrolysis
24~36h of reaction is closed, clear solution is obtained；
Step 3: the clear solution that step 2 is obtained carries out concentrated by rotary evaporation, and ethyl alcohol is added and is precipitated, and filters i.e. much ammonia third
Base cage modle polysilsesquioxane.
2. a kind of synthetic method of more aminopropyl cage type polysilsesquioxanes according to claim 1, it is characterised in that: step
In rapid one, the volume ratio of the aminopropyl front three/Ethoxysilane and methanol solution is 12:1.
3. a kind of synthetic method of more aminopropyl cage type polysilsesquioxanes according to claim 1, it is characterised in that: step
In rapid one, the rate of addition of the aminopropyl front three/Ethoxysilane is controlled in 20 drops/min.
4. a kind of synthetic method of more aminopropyl cage type polysilsesquioxanes according to claim 1, it is characterised in that: step
In rapid two, the concentration of the hydrochloric acid is 10vol.%~37vol.%.
5. a kind of synthetic method of more aminopropyl cage type polysilsesquioxanes according to claim 1, it is characterised in that: step
In rapid two, the hydrochloric acid is 2:13 with the volume ratio of methanol and aminopropyl front three/Ethoxysilane mixed solution.
6. a kind of synthetic method of more aminopropyl cage type polysilsesquioxanes according to claim 1, it is characterised in that: step
In rapid three, the temperature of the concentrated by rotary evaporation is 40~60 DEG C, and the volume after concentration is the 1/4~1/2 of original volume.
7. a kind of synthetic method of more aminopropyl cage type polysilsesquioxanes according to claim 1, it is characterised in that: step
In rapid three, the volume ratio of more aminopropyl POSS and ethyl alcohol in the clear solution are 1:1 or 1:2.
8. a kind of synthesis side of more aminopropyl cage type polysilsesquioxanes described in any claim according to claim 1~7
Method, it is characterised in that: further include step 4: being dissolved more aminopropyl POSS using methanol, and more aminopropyl POSS are mixed after dissolution
Closing the concentration in solution is 0.1g/ml, is then rotated to the 1/4~1/2 of original volume, and ethyl alcohol is added and is precipitated, more aminopropyls
The volume ratio of POSS and ethyl alcohol is 1:1 or 1:2, repeats 3~5 times to get more aminopropyl POSS are arrived.
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Cited By (3)
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| 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 |
| CN113437361A (en) * | 2021-05-28 | 2021-09-24 | 浙江工业大学 | Polymer electrolyte membrane containing octaaminopropyl POSS hydrochloride and preparation method and application thereof |
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Application publication date: 20191122 |