CN105236428B - Wormlike hollow silicon dioxide and preparation method thereof - Google Patents
Wormlike hollow silicon dioxide and preparation method thereof Download PDFInfo
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- CN105236428B CN105236428B CN201510559042.3A CN201510559042A CN105236428B CN 105236428 B CN105236428 B CN 105236428B CN 201510559042 A CN201510559042 A CN 201510559042A CN 105236428 B CN105236428 B CN 105236428B
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Abstract
The invention discloses a wormlike hollow silicon dioxide being composed of, by mass, 0.1-0.5 parts of an organic silane coupling agent, 50-100 parts of deionized water and 0.5-1.0 part of tetraethylortho silicate. The invention also provides a preparation method of the wormlike hollow silicon dioxide, which includes the steps of pre-hydrolyzing the organic silane coupling agent through sol-gel method, and then adding the tetraethylortho silicate and concentrated ammonia water to perform a reaction under an alkaline condition to obtain the wormlike hollow silicon dioxide. The wormlike hollow silicon dioxide is simple in preparation method, is strong in operability, is mild in reaction conditions, achieves one-step functionalization and has excellent application prospect.
Description
Technical field
The invention belongs to chemical field, is related to a kind of silicon dioxide, a kind of specifically vermiform hollow silicon dioxide
And preparation method thereof.
Background technology
Silicon dioxide has good mechanical performance, heat stability and chemical inertness, is all the time scientific and technical neck
One of focus of domain research.It is always a kind of important Inorganic Chemicals, and silicate glass is in science and industrial technology
Extremely important role is play always；On the other hand, as filling enhancing modified agent, it is widely used in rubber, plastics, fiber
In industry.1956, Kolbe in short chain alcoholic solvent, synthesized first non-porous, single dispersing two by silanol salt hydrolysiss, polymerization
After silicon oxide particle, up till now, earth silicon material has become study hotspot.
And the material of hollow ball structure is due to property such as its potential micro- surface area, void content, heat conductivity, optical indexs
The extensive concern of people can have been attracted.Wherein, silicon dioxide is because its unique characteristic, such as：Density is low and high mechanical strength, changes
The features such as learning stable in properties, heat stability is very strong, can be applicable to the release of medicine and biomolecule, photocatalysis, energy storage, sensing control
System release etc..Silicon dioxide hollow material structure common at present is mostly spherical, and surface is hydroxyl, and the later stage must adopt organic
Silane coupler carries out again functionalization to silicon dioxide hollow material surface（Yu Shuhong, Wan Yong, a kind of hollow silica ball
Preparation method, CN1931718A；Zheng Nanfeng, Fang Xiaoliang, Chen Cheng, Li Yue, a kind of preparation method of ordered mesoporous silica dioxide,
CN102153094A）.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of vermiform hollow silicon dioxide and its system
Preparation Method, described this vermiform hollow silicon dioxide and preparation method thereof solve silicon dioxide hollow material in prior art
The technical problem that material surface is hydroxyl, be of limited application.
The invention provides a kind of vermiform hollow silicon dioxide, calculates according to the mass fraction, its raw material composition and content are such as
Under：
Organo silane coupling agent 0.1-0.5 parts,
Deionized water 50-100 parts,
Tetraethyl orthosilicate 0.5-1.0 parts.
Further, described organo silane coupling agent be vinyltrimethoxy silane, phenyltrimethoxysila,e or
Person's (3- mercaptopropyis) trimethoxy silane.
Present invention also offers a kind of preparation method of above-mentioned vermiform hollow silicon dioxide, comprises the steps：
1) organo silane coupling agent, deionized water and tetraethyl orthosilicate are weighed according to mass fraction；
2) organo silane coupling agent is added in deionized water, stirring at normal temperature 30-40min under 300-400r/min,
50-60 DEG C is warming up to, 0.5～3h is hydrolyzed；
3) tetraethyl orthosilicate is added into step 2）Aqueous solution in, and while add ammonia adjust pH be 9-12, continue control
Speed of agitator processed is 300-400r/min, and stirring reaction 3-7h obtains final product vermiform hollow silicon dioxide.
Specifically, the mass percent concentration of described ammonia is 25%.
The present invention adopts sol-gel process, by organo silane coupling agent and the hydrolysis-condensation reaction system of tetraethyl orthosilicate
For constitutionally stable vermiform silicon dioxide hollow material, the specific surface area of hollow silica ball is effectively increased；And
Can be to vermiform silicon dioxide hollow material functionalization, the hollow material contains the functionalization group that can be used effectively, such as second
Thiazolinyl, phenyl, sulfydryl, expand to a great extent the application of the hollow material, with potential using value.
The present invention is compared with prior art, and its technological progress is significant.The present invention makes organosilicon by sol-gel process
The prehydrolysis of alkane coupling agent elder generation, are subsequently added tetraethyl orthosilicate and strong aqua ammonia react in the basic conditions, obtain vermiform hollow two
Silicon oxide.The preparation process is simple of the vermiform hollow silicon dioxide, workable, reaction condition is gentle, and is capable of achieving
Functionalization to the step of hollow silicon dioxide one, has a good application prospect.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of the vermiform hollow silicon dioxide obtained by the method for the present invention.
Specific embodiment
The present invention is described in further detail below by embodiment, but is not intended to limit the present invention.
Embodiment 1
A kind of vermiform hollow silicon dioxide, calculates according to the mass fraction, and its raw material composition and content are as follows：
0.1 part of (3- mercaptopropyis) trimethoxy silane,
50 parts of deionized water,
0.5 part of tetraethyl orthosilicate.
A kind of preparation method of above-mentioned vermiform hollow silicon dioxide is as follows：
0.1 part of (3- mercaptopropyis) trimethoxy silane is added in 50 parts of deionized waters, the room temperature under 300r/min
Stirring 30min, is warming up to 50 DEG C, hydrolyzes 1h；Subsequently 0.5 part of tetraethyl orthosilicate is added thereto, and while adds 10ul mass
It is 9 that the ammonia of fraction 25% adjusts pH, and it is 300r/min that continuation controls speed of agitator, and stirring reaction 3h obtains final product vermiform hollow two
Silicon oxide.
Obtained sample is tested by the H-800 types transmission electron microscope of Li companies, and the hollow material 80% is in compacted
Worm shape hollow-core construction.
Embodiment 2
A kind of vermiform hollow silicon dioxide, calculates according to the mass fraction, and its raw material composition and content are as follows：
0.2 part of vinyl trimethylsilane
50 parts of deionized water
1 part of tetraethyl orthosilicate
A kind of preparation method of above-mentioned vermiform hollow silicon dioxide is as follows：
0.2 part of vinyl trimethylsilane is added in 50 parts of deionized waters, the stirring at normal temperature under 400r/min
30min, is warming up to 60 DEG C, hydrolyzes 30min；Subsequently 1 part of tetraethyl orthosilicate is added thereto, and while adds 20ul mass fractions
It is 10 that 25% ammonia adjusts pH, and it is 400r/min that continuation controls speed of agitator, and stirring reaction 7h obtains final product the hollow dioxy of vermiform
SiClx.
Obtained sample is tested by the H-800 types transmission electron microscope of Li companies, and the hollow material is into sky
Heart vermiform, as shown in Figure 1.
Embodiment 3
A kind of vermiform hollow silicon dioxide, calculates according to the mass fraction, and its raw material composition and content are as follows：
0.3 part of vinyl trimethylsilane
80 parts of deionized water
0.8 part of tetraethyl orthosilicate
A kind of preparation method of above-mentioned vermiform hollow silicon dioxide is as follows：
0.3 part of vinyl trimethylsilane is added in 80 parts of deionized waters, stirring at normal temperature 1h under 400r/min, is risen
Temperature hydrolyzes 2h to 50 DEG C；Subsequently 0.8 part of tetraethyl orthosilicate is added thereto, and while adds the ammonia of 30ul mass fractions 25%
It is 11 to adjust pH, and it is 400r/min that continuation controls speed of agitator, and stirring reaction 5h obtains final product vermiform hollow silicon dioxide.
Obtained sample is tested by the H-800 types transmission electron microscope of Li companies, and the hollow material 70% is anthelmintic
Shape hollow-core construction.
Embodiment 4
A kind of vermiform hollow silicon dioxide, calculates according to the mass fraction, and its raw material composition and content are as follows：
0.4 part of phenyltrimethoxysila,e
100 parts of deionized water
1.0 parts of tetraethyl orthosilicate
A kind of preparation method of above-mentioned vermiform hollow silicon dioxide is as follows：
0.4 part of phenyltrimethoxysila,e is added in 100 parts of deionized waters, stirring at normal temperature 1h under 400r/min,
60 DEG C are warming up to, 3h is hydrolyzed；Subsequently 1 part of tetraethyl orthosilicate is added thereto, and while adds the ammonia of 40ul mass fractions 25%
It is 12 to adjust pH, and it is 400r/min that continuation controls speed of agitator, and stirring reaction 6h obtains final product vermiform hollow silicon dioxide.
Obtained sample is tested by the H-800 types transmission electron microscope of Li companies, and the hollow material is anthelmintic
Shape hollow-core construction.
Embodiment 5
Take the cyclamen aldehyde ethanol solution that 50ml concentration is 5g/L to be placed in conical flask, add the vermiform in embodiment 2
Hollow silicon dioxide 0.1g, shakes 24h with constant temperature oscillator at room temperature, and 10min is centrifuged with 10000r/min, takes supernatant
Absorbance is tested using UV2100 ultraviolet spectrophotometers.
50ml ethanol solution is separately taken, the vermiform hollow silicon dioxide 0.1g in embodiment 2 is added, at room temperature with constant temperature
24h is shaken in agitator, 10min is centrifuged with 10000r/min, take supernatant as blank reference.
Above-mentioned load issue shows that the vermiform hollow silicon dioxide is 39.98% to the load factor of cyclamen aldehyde.
Claims (2)
1. a kind of preparation method of vermiform hollow silicon dioxide, it is characterised in that comprise the steps：
1）Organo silane coupling agent, deionized water and tetraethyl orthosilicate are weighed according to mass fraction；
Organo silane coupling agent 0.1-0.5 parts,
Deionized water 50-100 parts,
Tetraethyl orthosilicate 0.5-1.0 parts；
Described organo silane coupling agent is vinyltrimethoxy silane, phenyltrimethoxysila,e or (3- sulfydryls third
Base) trimethoxy silane；
2）Organo silane coupling agent is added in deionized water, stirring at normal temperature 30-40min under 300-400r/min, is heated up
To 50-60 DEG C, 0.5～3h is hydrolyzed；
3）Tetraethyl orthosilicate is added into step 2）Aqueous solution in, and while add ammonia adjust pH be 9-12, continue control stir
Mix rotating speed is 300-400r/min, and stirring reaction 3-7h obtains final product vermiform hollow silicon dioxide.
2. the preparation method of a kind of vermiform hollow silicon dioxide according to claim 1, it is characterised in that：Described ammonia
The mass percent concentration of water is 25%.
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| CN109607552B (en) * | 2019-01-15 | 2021-10-22 | 河北工业大学 | Method for preparing silicon dioxide with three-dimensional ball chain structure |
| CN115215348B (en) * | 2022-08-29 | 2023-11-17 | 吉林大学 | Preparation method of vermicular mesoporous silica |
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