CN104530116B - The preparation method of shortrange order cage modle aminopropyl silsesquioxane spheroidal particle - Google Patents
The preparation method of shortrange order cage modle aminopropyl silsesquioxane spheroidal particle Download PDFInfo
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- CN104530116B CN104530116B CN201510025219.1A CN201510025219A CN104530116B CN 104530116 B CN104530116 B CN 104530116B CN 201510025219 A CN201510025219 A CN 201510025219A CN 104530116 B CN104530116 B CN 104530116B
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- trimesic acid
- aminopropyltrimethoxysilane
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Abstract
The preparation method of shortrange order cage modle aminopropyl silsesquioxane spheroidal particle of the present invention, belong to field of material technology, specifically related to a kind of preparation method of the spherical aminopropyl silsesquioxane particles with shot-range ordered structure, aminopropyl silsesquioxane particles prepared by this method can be used for the removing of metal ion in solution and the absorption of carbon dioxide；A kind of preparation method for the shortrange order cage modle aminopropyl silsesquioxane spheroidal particle that the easy to operate, reaction time is short, reaction condition is gentle is provided；Follow the steps below：The dewater treatment of Trimesic acid, the preparation of the ethanol solution of γ aminopropyl trimethoxysilanes, hydrolysis-condensation reaction, alkali cleaning；Present invention is mainly applied to the fields such as adsorbing separation, drug delivery, modified-high polymer.
Description
Technical field
The preparation method of shortrange order cage modle aminopropyl silsesquioxane spheroidal particle of the present invention, belongs to material technology neck
Domain, and in particular to a kind of preparation method of the spherical aminopropyl silsesquioxane particles with shot-range ordered structure, this method
The aminopropyl silsesquioxane particles of preparation can be used for the removing of metal ion in solution and the absorption of carbon dioxide.
Background technology
Cage modle polysilsesquioxane formula is (RSiO1.5) n, the organic group that wherein R is connected by eight drift angle Si atoms
Group, common R bases are vinyl, epoxy radicals, amino, phenyl isoreactivity or inertia group.The cage modle of cage modle polysilsesquioxane
Frame structure causes it to have good dielectricity and optical property, is widely used in exotic material, fire proofing, electricity absolutely
A kind of fields such as edge material, EL material and modified traditional superpolymer performance, it has also become novel silicon with development prospect
Base hydridization functional material.
At present, cage modle polysilsesquioxane is mainly prepared by sol-gel process, i.e., under acid or base catalyst effect,
Obtained by the hydrolysis-condensation reaction of trichlorosilane or trialkoxy silane.Prepare the main side of the silsesquioxane containing aminophenyl
Method is to prepare times rod siloxanes containing phenyl by the hydrolytic condensation of the body of organic polysiloxane precursor containing phenyl first, then carry out
Nitrification, then by catalysis reduction, obtain cage-type silsesquioxane containing aminophenyl.For example, remaining ancient cooking vessel sound etc. is with alkaline reducer benzene
Eight nitrobenzophenone times rod siloxanes under Fe/C catalysis, are reduced to aminophenyl silsesquioxane by hydrazine.Gu Zheming etc. uses ammonia
Propyl-triethoxysilicane is raw material, adds deionized water, under hydrochloric acid catalysis, reacts 72 hours in 60 DEG C in hexamethylene, so
Solvent is removed by rotary evaporation afterwards, the cage modle aminopropyl silsesquioxane that yield is 80% is successfully prepared.Li Qi side etc. is with industry
The aminopropyl trimethoxy siloxane of change is raw material, and tetramethyl aqua ammonia is catalyst, through hydrolytic condensation in alcohols solvent
Directly prepare amino cage-type silsesquioxane.
In prior synthesizing method, reaction system is homogeneous reaction system, and most of prepared product does not have well-regulated
Pattern and structure.It is well known that pattern and structure have very important influence for the physico-chemical property of Micron-nano composites.
Therefore, preparing the cage modle polysilsesquioxane with regular morphology and ordered structure has very important theory value and practicality
Value.In summary, it is necessary to which prior art is improved.
The content of the invention
In order to overcome the shortcomings of that there is provided a kind of easy to operate, reaction time is short, reaction condition temperature in the presence of prior art
The preparation method of the shortrange order cage modle aminopropyl silsesquioxane spheroidal particle of sum.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：
The preparation method of shortrange order cage modle aminopropyl silsesquioxane spheroidal particle, is followed the steps below：Equal three
The dewater treatment of benzoic acid, the preparation of the ethanol solution of γ-aminopropyltrimethoxysilane, hydrolysis-condensation reaction, alkali cleaning.
The dewater treatment of the Trimesic acid is concretely comprised the following steps：Trimesic acid is placed in baking oven, in 80 DEG C of heating
It is dehydrated 2h.
The preparation of the ethanol solution of the γ-aminopropyltrimethoxysilane is concretely comprised the following steps：20mL absolute ethyl alcohols are added
Enter in 50mL three-necked flasks, then measure 1mL γ-aminopropyltrimethoxysilanes and add in the flask, seal, use agitator
180 revs/min of 30~50min of stirring.
The hydrolysis-condensation reaction is concretely comprised the following steps：The Trimesic acid after dewater treatment is weighed, γ-ammonia of configuration is added
In the ethanol solution of propyl trimethoxy silicane, stirring 30min to solid is completely dissolved, and then adds 0.3mL ammonia spirit,
Continue to stir and stop stirring after 10min, stand reaction 24h, by centrifuging, obtain white solid, as hydrolytic condensation is produced
Thing.
The Trimesic acid and the mol ratio of γ-aminopropyltrimethoxysilane are 1：1-3, the pH of ammonia spirit is 9-
11。
The Trimesic acid and the mol ratio of γ-aminopropyltrimethoxysilane are 1：3, the pH of ammonia spirit is 10.
The alkali cleaning is concretely comprised the following steps：By hydrolysis-condensation reaction obtain hydrolysis condensation product pH be 10 ammonia spirit from
The heart is washed 3-4 time, then with ethanol centrifuge washing 2-3 times, will be centrifuged product and is placed in vacuum drying chamber in 40 DEG C of drying process
2h, produces this product.
The present invention have the advantage that compared with prior art for：
The present invention is exogenous molecules using Trimesic acid, have adjusted γ-aminopropyltrimethoxysilane in alcohol solvent
Hydrolytic condensation behavior, is prepared for the hydrolysis condensation product of γ-aminopropyltrimethoxysilane Trimesic acid salt；By alkali cleaning,
Trimesic acid is removed, shortrange order cage modle aminopropyl silsesquioxane spheroidal particle is obtained；Reaction system is simple and easy to apply, anti-
Answer mild condition, yield height, be easy to large-scale production；Using the aminopropyl silsesquioxane spheroidal particle prepared by the present invention,
Average diameter is 3~5 μm, with shortrange order structure, available for fields such as adsorbing separation, drug delivery, modified-high polymers.
Brief description of the drawings
The embodiment of the present invention is described in further detail below by accompanying drawing.
Fig. 1 is the electron scanning micrograph in the embodiment of the present invention 1；
Fig. 2 is Fig. 1 partial enlarged drawing；
Fig. 3 is the infrared spectrogram of the embodiment of the present invention 1；
Fig. 4 is the XRD diffracting spectrums of the embodiment of the present invention 1；
Fig. 5 is the transmission electron microscope photo of the embodiment of the present invention 1.
Embodiment
The invention will be further described for example below combination accompanying drawing.
Embodiment 1
1st, the dewater treatment of Trimesic acid
Trimesic acid is placed in baking oven, in 80 DEG C of thermal dehydration 2h.
2nd, the ethanol solution of γ-aminopropyltrimethoxysilane is prepared
20mL absolute ethyl alcohols are added in 50mL three-necked flasks, the addition of 1mL γ-aminopropyltrimethoxysilanes is then measured
In flask, sealing, with 180 revs/min of 30~50min of stirring of agitator, the ethanol that γ-aminopropyltrimethoxysilane is made is molten
Liquid.
3rd, hydrolysis-condensation reaction
The Trimesic acid of step 1 preparation is weighed, the ethanol of γ-aminopropyltrimethoxysilane prepared by step 2 is added
In solution, the mol ratio of Trimesic acid and γ-aminopropyltrimethoxysilane is 1：3, stirring 30min is completely molten to solid
Solution.Then, add 0.3mLpH be 10 ammonia spirit, continue stir 10min after stop stirring, stand reaction 24h, by from
The heart is separated, and obtains white solid, as hydrolysis condensation product.
4th, alkali cleaning
With pH it is 10 ammonia spirit centrifuge washing 3~4 times by the hydrolysis condensation product obtained by step 3, then uses second
Alcohol centrifuge washing 2~3 times.Centrifugation product is placed in vacuum drying chamber in 40 DEG C of drying process 2h, shortrange order is prepared
Cage modle aminopropyl silsesquioxane spheroidal particle.
Embodiment 2
1st, the dewater treatment of Trimesic acid
Trimesic acid is placed in baking oven, in 80 DEG C of thermal dehydration 2h.
2nd, the ethanol solution of γ-aminopropyltrimethoxysilane is prepared
20mL absolute ethyl alcohols are added in 50mL three-necked flasks, the addition of 1mL γ-aminopropyltrimethoxysilanes is then measured
In flask, sealing, with 180 revs/min of 30~50min of stirring of agitator, the ethanol that γ-aminopropyltrimethoxysilane is made is molten
Liquid.
3rd, hydrolysis-condensation reaction
The Trimesic acid of step 1 preparation is weighed, the ethanol of γ-aminopropyltrimethoxysilane prepared by step 2 is added
In solution, the mol ratio of Trimesic acid and γ-aminopropyltrimethoxysilane is 1：1, stirring 30min is completely molten to solid
Solution；Then, add 0.3mLpH be 10 ammonia spirit, continue stir 10min after stop stirring, stand reaction 24h, by from
The heart is separated, and obtains white solid, as hydrolysis condensation product.
4th, alkali cleaning
With pH it is 10 ammonia spirit centrifuge washing 3~4 times by the hydrolysis condensation product obtained by step 3, then uses second
Alcohol centrifuge washing 2~3 times, centrifugation product is placed in vacuum drying chamber in 40 DEG C of drying process 2h, shortrange order is prepared
Cage modle aminopropyl silsesquioxane spheroidal particle.
Embodiment 3
1st, the dewater treatment of Trimesic acid
Trimesic acid is placed in baking oven, in 80 DEG C of thermal dehydration 2h.
2nd, the ethanol solution of γ-aminopropyltrimethoxysilane is prepared
20mL absolute ethyl alcohols are added in 50mL three-necked flasks, the addition of 1mL γ-aminopropyltrimethoxysilanes is then measured
In flask, sealing, with 180 revs/min of 30~50min of stirring of agitator, the ethanol that γ-aminopropyltrimethoxysilane is made is molten
Liquid.
3rd, hydrolysis-condensation reaction
The Trimesic acid of step 1 preparation is weighed, the ethanol of γ-aminopropyltrimethoxysilane prepared by step 2 is added
In solution, the mol ratio of Trimesic acid and γ-aminopropyltrimethoxysilane is 1：2, stirring 30min is completely molten to solid
Solution；Then, add 0.3mLpH be 10 ammonia spirit, continue stir 10min after stop stirring, stand reaction 24h, by from
The heart is separated, and obtains white solid, as hydrolysis condensation product.
4th, alkali cleaning
With pH it is 10 ammonia spirit centrifuge washing 3~4 times by the hydrolysis condensation product obtained by step 3, then uses second
Alcohol centrifuge washing 2~3 times, centrifugation product is placed in vacuum drying chamber in 40 DEG C of drying process 2h, shortrange order is prepared
Cage modle aminopropyl silsesquioxane spheroidal particle.
Embodiment 4
1st, the dewater treatment of Trimesic acid
Trimesic acid is placed in baking oven, in 80 DEG C of thermal dehydration 2h.
2nd, the ethanol solution of γ-aminopropyltrimethoxysilane is prepared
20mL absolute ethyl alcohols are added in 50mL three-necked flasks, the addition of 1mL γ-aminopropyltrimethoxysilanes is then measured
In flask, sealing, with 180 revs/min of 30~50min of stirring of agitator, the ethanol that γ-aminopropyltrimethoxysilane is made is molten
Liquid.
3rd, hydrolysis-condensation reaction
The Trimesic acid of step 1 preparation is weighed, the ethanol of γ-aminopropyltrimethoxysilane prepared by step 2 is added
In solution, the mol ratio of Trimesic acid and γ-aminopropyltrimethoxysilane is 1：3, stirring 30min is completely molten to solid
Solution；Then, the ammonia spirit that 0.3mLpH is 9 is added, continues to stir stopping stirring after 10min, reaction 24h is stood, passes through centrifugation
Separation, obtains white solid, as hydrolysis condensation product.
4th, alkali cleaning
With pH it is 10 ammonia spirit centrifuge washing 3~4 times by the hydrolysis condensation product obtained by step 3, then uses second
Alcohol centrifuge washing 2~3 times, centrifugation product is placed in vacuum drying chamber in 40 DEG C of drying process 2h, shortrange order is prepared
Cage modle aminopropyl silsesquioxane spheroidal particle.
Embodiment 5
1st, the dewater treatment of Trimesic acid
Trimesic acid is placed in baking oven, in 80 DEG C of thermal dehydration 2h.
2nd, the ethanol solution of γ-aminopropyltrimethoxysilane is prepared
20mL absolute ethyl alcohols are added in 50mL three-necked flasks, the addition of 1mL γ-aminopropyltrimethoxysilanes is then measured
In flask, sealing, with 180 revs/min of 30~50min of stirring of agitator, the ethanol that γ-aminopropyltrimethoxysilane is made is molten
Liquid.
3rd, hydrolysis-condensation reaction
The Trimesic acid of step 1 preparation is weighed, the ethanol of γ-aminopropyltrimethoxysilane prepared by step 2 is added
In solution, the mol ratio of Trimesic acid and γ-aminopropyltrimethoxysilane is 1：3, stirring 30min is completely molten to solid
Solution；Then, add 0.3mLpH be 11 ammonia spirit, continue stir 10min after stop stirring, stand reaction 24h, by from
The heart is separated, and obtains white solid, as hydrolysis condensation product.
4th, alkali cleaning
With pH it is 10 ammonia spirit centrifuge washing 3~4 times by the hydrolysis condensation product obtained by step 3, then uses second
Alcohol centrifuge washing 2~3 times, centrifugation product is placed in vacuum drying chamber in 40 DEG C of drying process 2h, shortrange order is prepared
Cage modle aminopropyl silsesquioxane spheroidal particle.
In order to verify beneficial effects of the present invention, inventor is to the shortrange order cage modle ammonia prepared by the embodiment of the present invention 1
Propylsilsesquioxane spheroidal particle is carried out using SEM, Fourier transformation infrared spectrometer and XRD diffractometers
Observation experiment, various test situations are as follows：
Observe article：Shortrange order cage modle aminopropyl silsesquioxane spheroidal particle.
Laboratory apparatus：SEM, model XL-20 is produced by Philips companies of Britain；Fourier transform
Infrared spectrometer, model AVTAR360 is produced by Nicolet companies；Material crystal formation is spread out by the full-automatic X-rays of D/Max-3c
Instrument measure is penetrated, measure angular range is 3 θ -50 θ, and copper target is determined（40 kV and 30 mA）, size and pattern pass through Hitachi
H-600 type transmission electron microscope observations, the kV of accelerating potential 10.
1st, observe
By SEM and the method for testing of transmission electron microscope to shortrange order cage modle aminopropyl sesquialter silicon
Oxygen alkane spheroidal particle is observed.
2nd, test
By Fourier transformation infrared spectrometer and XRD diffractometers method of testing to shortrange order cage modle aminopropyl silsesquioxane
Alkane spheroidal particle is tested.
3rd, observed result
The electron scanning micrograph of shortrange order cage modle aminopropyl silsesquioxane spheroidal particle is shown in Fig. 1, its part
Magnified sweep electromicroscopic photograph is shown in Fig. 2.FFIR curve is shown in Fig. 3, and XRD diffraction analysis is shown in Fig. 4.Transmitted electron shows
Micro mirror photo is shown in Fig. 5.
Shortrange order cage modle aminopropyl silsesquioxane spheroidal particle scanning electron photo prepared by Fig. 1 and Fig. 2 displays.Knot
Fruit shows that spherical structure, a diameter of 3~5 microns is integrally presented in prepared particulate.
Fig. 3 is shortrange order cage modle aminopropyl silsesquioxane spheroidal particle infrared spectrum spectrogram, it can be seen that
1020cm-1Locate outside for Si-O-Si feature stretching vibration peaks, 1430cm-1Locate the absworption peak for amino, confirmation has obtained ammonia third
Base silsesquioxane particles.
Fig. 4 is the XRD diffraction spectrograms of shortrange order cage modle aminopropyl silsesquioxane spheroidal particle, and diffraction maximum is special from figure
Levy as can be seen that prepared aminopropyl silsesquioxane spheroidal particle is shot-range ordered structure.
Fig. 5 is the transmission electron microscope photo of shortrange order cage modle aminopropyl silsesquioxane spheroidal particle, can from figure
Go out, prepared aminopropyl silsesquioxane spheroidal particle has spherical morphology, with three-dimensional open-framework.
Claims (3)
1. the preparation method of shortrange order cage modle aminopropyl silsesquioxane spheroidal particle, it is characterised in that according to following steps
Carry out：The dewater treatment of Trimesic acid, the preparation of the ethanol solution of γ-aminopropyltrimethoxysilane, hydrolysis-condensation reaction,
Alkali cleaning；The dewater treatment of the Trimesic acid is concretely comprised the following steps：Trimesic acid is placed in baking oven, in 80 DEG C of thermal dehydrations
2h；The preparation of the ethanol solution of the γ-aminopropyltrimethoxysilane is concretely comprised the following steps：20mL absolute ethyl alcohols are added into 50mL
In three-necked flask, then measure 1mL γ-aminopropyltrimethoxysilanes and add in the flask, seal, with 180 revs/min of agitator
Clock stirs 30~50min；The hydrolysis-condensation reaction is concretely comprised the following steps：The Trimesic acid after dewater treatment is weighed, addition is matched somebody with somebody
In the ethanol solution for the γ-aminopropyltrimethoxysilane put, stirring 30min to solid is completely dissolved, and then adds 0.3mL's
Ammonia spirit, continues to stir stopping stirring after 10min, stands reaction 24h, by centrifuging, obtains white solid, as water
Solve condensation product；The alkali cleaning is concretely comprised the following steps：Hydrolysis-condensation reaction is obtained into the ammoniacal liquor that hydrolysis condensation product pH is 10 molten
Liquid centrifuge washing 3-4 times, then with ethanol centrifuge washing 2-3 times, centrifugation product is placed in vacuum drying chamber in 40 DEG C of dryings
2h is handled, this product is produced.
2. the preparation method of shortrange order cage modle aminopropyl silsesquioxane spheroidal particle according to claim 1, it is special
Levy and be：The Trimesic acid and the mol ratio of γ-aminopropyltrimethoxysilane are 1：1-3, the pH of ammonia spirit is 9-
11。
3. the preparation method of shortrange order cage modle aminopropyl silsesquioxane spheroidal particle according to claim 2, it is special
Levy and be：The Trimesic acid and the mol ratio of γ-aminopropyltrimethoxysilane are 1：3, the pH of ammonia spirit is 10.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503419A (en) * | 2009-03-20 | 2009-08-12 | 北京化工大学 | Octa-aminopropyl cage type sesquialter siloxane and preparation thereof |
| CN102642840A (en) * | 2012-05-10 | 2012-08-22 | 陕西师范大学 | Preparation method of spherical silicon dioxide particles with three-dimensional laminated structure |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503419A (en) * | 2009-03-20 | 2009-08-12 | 北京化工大学 | Octa-aminopropyl cage type sesquialter siloxane and preparation thereof |
| CN102642840A (en) * | 2012-05-10 | 2012-08-22 | 陕西师范大学 | Preparation method of spherical silicon dioxide particles with three-dimensional laminated structure |
Non-Patent Citations (3)
| Title |
|---|
| Synthesis and Characterization of Novel Hyperbranched Polyimides Based on Silsesquioxane Nanocomposite Networks;Turgay SECKIN等;《Turk. J. Chem.》;20051231;第29卷(第1期);第49-59页 * |
| 基于主客体作用研究柠檬酸分子对APTES水解缩合行为的影响;宋少飞等;《中国化学会第十四届胶体与界面化学会议论文摘要集-第2分会：溶液中的聚集与分子组装》;CNKI;20130721;第189页 * |
| 有机酸与APTES超分子作用体系的水解缩合行为研究;宋少飞;《陕西师范大学博士学位论文》;CNKI;20140715;第45-47,60-67页 * |
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Inventor after: Zhou Fulin Inventor after: Song Shaofei Inventor after: Li Ping Inventor after: Gong Qiaojuan Inventor after: Xue Nana Inventor after: Lv Baohua Inventor before: Song Shaofei Inventor before: Zhou Fulin Inventor before: Li Ping Inventor before: Gong Qiaojuan Inventor before: Xue Nana Inventor before: Lv Baohua |
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