CN104860320B - A kind of preparation method of modified manometer silicon dioxide - Google Patents
A kind of preparation method of modified manometer silicon dioxide Download PDFInfo
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Abstract
The invention provides a kind of preparation method of modified manometer silicon dioxide, first, present invention addition shitosan makes the as far as possible few reunion in nucleation process of nano silicon, and the modified manometer silicon dioxide obtained from is homogeneous, stable, good dispersion.Second, disodium ethylene diamine tetraacetate and nanometer titanium dioxide pasc reaction make a certain amount of amino of its surface modification.3rd, nanometer titanium dioxide outer silicon has silanol and silicon amino, and the stannous chloride for adding makes silanol and silicon amino have activity very high to epoxy radicals, the process of reaction is accelerated, while greatly improving the grafting rate of surface modification of silica.
Description
Technical field
The present invention relates to technical field of nano material, more particularly to a kind of preparation method of modified manometer silicon dioxide.
Background technology
Nano silicon is unformed white powder, nontoxic, tasteless, pollution-free, is that a kind of surface has hydroxyl and suction
The nonmetallic materials of attached water.The molecule of nano silicon is in three-dimensional chain structure, with particle diameter it is small, density is low, specific surface area
Big the characteristics of, with superior stability, thickening property, extinction, anti-stickiness, reinforcing, thixotropy and excellent optics and machine
Tool performance, is widely used in the neck such as ceramics, rubber, plastics, electronic package material, anti-biotic material, coating, pigment and catalyst carrier
Domain.Because the performance of material is closely related with the particle size of material and pattern, many performances are only in the particle size of material
When uniform with shape can macroscopically showing, therefore control material granule size and pattern, prepare have it is uniform
The single dispersing material of size and regular morphology is the study hotspot in present material science.
At present, the preparation technology of nano silicon is divided into the major class of dry and wet two, wherein, dry method is primarily referred to as gas phase
Method, warm therapy includes chemical precipitation method, sol-gel process, hydro-thermal method and microemulsion method.Vapor phase method is general with silicon tetrachloride as former
Material, silicon tetrachloride gas is hydrolyzed under hydrogen, oxygen stream high temperature, prepares nano silicon.The method can prepare pure
Degree is high, surface hydroxyl is few, reinforcing good nano silicon, but energy resource consumption is big in process of production, and expensive starting materials are right
The requirement of equipment is also higher.
Chemical precipitation method is that silicate is obtained into titanium dioxide silicon wafer that is loose, being precipitated out with flocculent structure by being acidified
Body.The method production procedure is simple, and energy consumption is low, but is difficult to control the aperture shape of particle, and pore-size distribution is also very wide, uneven
It is even, poor activity.Sol-gal process is, with inorganic salts or metal alkoxide as predecessor, through the gradually gel of hydrolytie polycondensation process, to obtain
To nano silicon.The method is easy to operate, but relatively costly, easily causes environmental pollution, is unfavorable for industrialization.Microemulsion method
Preparing nano material has the characteristics of operating easy, but microemulsion method is vulnerable to examination during nano silicon is prepared
Test the influence of the factors such as condition, the nano silicon for obtaining it is dispersed poor.
The content of the invention
Present invention solves the technical problem that being to provide a kind of preparation method of modified manometer silicon dioxide, what is obtained is modified
Nano silicon is homogeneous, stable, good dispersion.
In view of this, the invention provides a kind of preparation method of modified manometer silicon dioxide, comprise the following steps：Step
A) hexamethylene, phenethyl phenol poly-oxypropylene polyoxyethylene ether, n-hexyl alcohol and Unigly GO 102S are mixed, micro emulsion is obtained after stirring
Liquid system；Step b) is adding deionized water, 1-2 mass parts shitosan and 2-6 mass parts just in the microemulsion system successively
Silester, stirring is dropwise added dropwise ammoniacal liquor, adds disodium ethylene diamine tetraacetate, and acetone is added after stirring, is subsequently adding 1,2 third
Glycol and deionized water are washed, and obtain nano silicon；The nano-silica that step c) obtains 2-8 mass parts steps b
SiClx is added into deionized water and alcohol mixed solution, and the polyethylene glycol of 5-8 mass parts is added after stirring, continues to stir, drop
Plus the metering system acid oxidase hydroxypropyl methyl dimethoxysilane of 1-2 mass parts, mixed solution is obtained after reaction；Step d) is to step
The stannous chloride of 1-2 mass parts is added in the mixed solution that rapid c is obtained, the methacrylic acid ring of 5-10 mass parts is added after stirring
Oxygen propyl ester, obtains modified manometer silicon dioxide after reaction.
Preferably, in step a), the hexamethylene is 100-120 mass parts, the phenethyl phenol polyoxypropylene polyoxy second
Alkene ether is 10-20 mass parts.
Preferably, in step a), the n-hexyl alcohol is 20-30 mass parts.
Preferably, in step a), the Unigly GO 102S is 10-15 mass parts.
Preferably, the mixing time of step a) is 10-15 minutes.
Preferably, in step b), the ammoniacal liquor is 1-3 mass parts.
Preferably, in step b), disodium ethylene diamine tetraacetate is 1-2 mass parts.
Preferably, in step b), the acetone is 50-80 mass parts.
Preferably, in step b), 1,2 propane diols is 5-10 mass parts.
Preferably, in step c), the deionized water is 100 mass parts, and ethanol is 200 mass parts.
The invention provides a kind of preparation method of modified manometer silicon dioxide, by hexamethylene, phenethyl phenol polyoxypropylene
The mixing of APEO, n-hexyl alcohol and Unigly GO 102S, obtains microemulsion system after stirring；Sequentially add deionized water, shell
Glycan and tetraethyl orthosilicate, stirring are dropwise added dropwise ammoniacal liquor, add disodium ethylene diamine tetraacetate, and acetone is added after stirring, wash,
Obtain nano silicon；The nano silicon that will be obtained is added into deionized water and alcohol mixed solution, is added after stirring
Enter polyethylene glycol, metering system acid oxidase hydroxypropyl methyl dimethoxysilane is added dropwise, reaction adds stannous chloride, adds after stirring
Enter GMA, modified manometer silicon dioxide is obtained after reaction.
Compared with prior art, first, present invention addition shitosan makes nano silicon as far as possible few in nucleation process
Reunion, the modified manometer silicon dioxide obtained from is homogeneous, stable, good dispersion.And have active in shitosan macromolecular
Hydroxyl and amino, they have stronger chemical reaction ability, and the hydroxyl on C-6 under conditions of alkalescence is more active.Shell gathers
The sugared hydroxyl of itself can be adsorbed onto the surface of newly formed nano silicon Si-OH, and its own abundant amino can promote instead
That answers accelerates.Second, disodium ethylene diamine tetraacetate and nanometer titanium dioxide pasc reaction make a certain amount of amino of its surface modification,
And inherently a kind of stabilizer of disodium ethylene diamine tetraacetate and compounding ingredient, when it is added dropwise ammoniacal liquor, teos hydrolysis
Process stabilization, therefore the nano silicon of production is relatively uniform, stable.3rd, nanometer titanium dioxide outer silicon have silanol and
Silicon amino, and the stannous chloride for adding makes silanol and silicon amino have activity very high to epoxy radicals, accelerates the process of reaction, together
When greatly improve the grafting rate of surface modification of silica.4th, nano silicon passes through glycidyl
After modified, its hydrophobicity in outer surface enhanced makes it can be difficult with dispersed, lasting stability in redisperse liquid
Reunite.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of modified manometer silicon dioxide prepared by the embodiment of the present invention 1.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of preparation method of modified manometer silicon dioxide, comprise the following steps：Step a)
Hexamethylene, phenethyl phenol poly-oxypropylene polyoxyethylene ether, n-hexyl alcohol and Unigly GO 102S are mixed, microemulsion is obtained after stirring
System；Step b) is successively to addition deionized water, 1-2 mass parts shitosan and the positive silicon of 2-6 mass parts in the microemulsion system
Acetoacetic ester, stirring, is dropwise added dropwise ammoniacal liquor, adds disodium ethylene diamine tetraacetate, and acetone is added after stirring, is subsequently adding 1,2 the third two
Alcohol and deionized water are washed, and obtain nano silicon；The nanometer titanium dioxide that step c) obtains 2-8 mass parts steps b
Silicon is added into deionized water and alcohol mixed solution, and the polyethylene glycol of 5-8 mass parts is added after stirring, continues to stir, and is added dropwise
The metering system acid oxidase hydroxypropyl methyl dimethoxysilane of 1-2 mass parts, obtains mixed solution after reaction；Step d) is to step
The stannous chloride of 1-2 mass parts is added in the mixed solution that c is obtained, the glycidyl of 5-10 mass parts is added after stirring
Propyl ester, obtains modified manometer silicon dioxide after reaction.
In step a), the phenethyl phenol poly-oxypropylene polyoxyethylene ether is surfactant, as breast in body series
Agent.Described Unigly GO 102S is cosurfactant, is a kind of long-chain fatty acid ester.
Preferably, the hexamethylene is preferably 100-120 mass parts, more preferably 105-115 mass parts；It is described
Phenethyl phenol poly-oxypropylene polyoxyethylene ether is preferably 10-20 mass parts, more preferably 12-16 mass parts；The n-hexyl alcohol is excellent
Elect 20-30 mass parts, more preferably 23-27 mass parts as；The Unigly GO 102S is preferably 10-15 mass parts, more preferably
It is 11-14 mass parts.The mixing time of step a) is preferably 10-15 minutes, more preferably 11-14 minutes.
In step b), after deionized water is added in the microemulsion system, preferably stirring 10-20 minutes, more preferably
12-18 minutes.In this step, the mixing time after 1-2 mass parts shitosan and 2-6 mass parts tetraethyl orthosilicates is added to be preferably
5-10 minutes, more preferably 6-8 minutes；The mixing time after disodium ethylene diamine tetraacetate is added to be preferably 1-2 hour.
According to the present invention, active hydroxyl and amino are contained in the shitosan macromolecular, it has stronger chemistry anti-
Should be able to power, the hydroxyl on C-6 under conditions of alkalescence is more active.The hydroxyl of shitosan itself can be adsorbed onto newly formed nanometer two
The surface of silica Si-OH, and its own abundant amino can promote accelerating for reaction.Therefore, in silica nucleation
During shitosan can be gathered in protective layer is formed around it, make the nano silicon to be formed more uniform and dispersiveness
It is good.
Disodium ethylene diamine tetraacetate is a kind of stabilizer and compounding ingredient, and it carries two carboxyls can be with silica surface
Concentration Si-OH is reacted, so as to modify a certain amount of amino group during nano silicon nucleation.And second two
Inherently a kind of stabilizer of amine tetraacethyl disodium and compounding ingredient, when it is added dropwise ammoniacal liquor, Hydrolysis of Ethyl Silicate stabilization,
Therefore the nano silicon of production is relatively uniform, stable.
It is above-mentioned be demulsified with acetone during, have the reunion of some nano silicons, for anti-phenomenon here, can be with
After demulsification, 1,2 propane diols are added to carry out ultrasonically treated.
Preferably, in step b), the ammoniacal liquor is preferably 1-3 mass parts, more preferably 2-3 mass parts；Second two
Amine tetraacethyl disodium is preferably 1-2 mass parts；The acetone is preferably 50-80 mass parts, more preferably 60-75 mass parts, more
Preferably 60-70 mass parts；1,2 propane diols is preferably 5-10 mass parts, more preferably 6-9 mass parts.
In step c), the polyethylene glycol increases whole system viscosity, nano silicon good dispersion, stability
It is high.Described metering system acid oxidase hydroxypropyl methyl dimethoxysilane makees silane coupler can modify nano silicon
Surface, and unsaturated bond in above-mentioned silane coupler with the ester group of GMA can be grafted it is anti-
Should.
Preferably, the step c is specially：By the nano silicon that 2-8 mass parts steps b is obtained add to
In deionized water and alcohol mixed solution, stir 5-10 minutes, add the polyethylene glycol of 5-8 mass parts, continue to stir 10 minutes,
The metering system acid oxidase hydroxypropyl methyl dimethoxysilane of 1-2 mass parts is added dropwise, reacts 10-30 minutes, obtain mixed solution.
In step c), the deionized water is preferably 100 mass parts, and ethanol is preferably 200 mass parts.
In step d), the stannous chloride promotes catalyst equivalent to one kind, silanol and silicon amino is had very epoxy radicals
Activity high, accelerates the process of reaction, and the grafting rate for also making its surface modified simultaneously is greatly improved.
Preferably, the step d) is specially：To addition 1-2 mass parts in the mixed solution that step c is obtained
Stannous chloride, is stirred 5-8 minutes, adds the GMA of 5-10 mass parts, and reaction is changed after 30-40 minutes
Property nano silicon.
Nano silicon by GMA it is modified after, its hydrophobicity in outer surface enhanced makes
It can be difficult to reunite with dispersed, lasting stability in redisperse liquid.
Preferably, after obtaining modified manometer silicon dioxide, preferred pair modified manometer silicon dioxide centrifuge washing is more
It is secondary.
From above scheme as can be seen that the method comprises the steps of firstly, preparing nano silicon, changing by classical microemulsion method
Enter, make preparation process highly stable；Then the nano silicon for preparing is modified, obtains modified manometer silicon dioxide.
The present invention has following features：
1 present invention adds the shitosan to make nano silicon in nucleation process, homogeneous, stable, good dispersion.
2nd, the disodium ethylene diamine tetraacetate and nanometer titanium dioxide pasc reaction for adding are so that a certain amount of ammonia of its surface modification
Base.
3rd, nanometer titanium dioxide outer silicon has silanol and silicon amino, and stannous chloride to both groups to methacrylic acid
The epoxy radicals of polyglycidyl has activity very high, and metering system acid oxidase hydroxypropyl methyl dimethoxysilane makees silane coupler
Also having undersaturated C=O and C=C keys can carry out graft reaction with GMA.
4th, nano silicon by GMA it is modified after, its hydrophobicity in outer surface enhanced,
It is set to be difficult to reunite with dispersed, lasting stability in redisperse liquid.
For a further understanding of the present invention, the technical scheme that the present invention is provided is carried out specifically with reference to embodiment
Bright, protection scope of the present invention is not limited by the following examples.
Tetraethyl orthosilicate (analysis is pure) in embodiment comes from Chemical Reagent Co., Ltd., Sinopharm Group；
Ethyl phenol polyoxyethylene polyoxypropylene ether in embodiment is emulsifying agent 12, from Lvshun chemical plant；
Unigly GO 102S in embodiment is cosurfactant, modelOLEIQUE CC 497
From good method lion (Shanghai) trade Co., Ltd；
Shitosan in embodiment comes from Chemical Reagent Co., Ltd., Sinopharm Group；
It is organic from leaf of speeding that metering system acid oxidase hydroxypropyl methyl dimethoxysilane in embodiment makees silane coupler
Silicon；
GMA in embodiment comes from the happy Industrial Co., Ltd.s of Shanghai Jin Jin；
Stannous chloride in embodiment comes from Weihui City Ya Xing Chemical Co., Ltd.s；
Polyethylene glycol model in embodiment can be PEG200 or PEG400, limited from Chinese medicines group chemical reagent
Company.
Embodiment 1
The present invention provides a kind of preparation method of nano silicon, comprises the following steps：
1. by the hexamethylene of 120 mass parts, the phenethyl phenol poly-oxypropylene polyoxyethylene ether of 20 mass parts, 20 mass parts
N-hexyl alcohol, the Unigly GO 102S of 12 mass parts are well mixed, and stir 15 minutes, in microemulsion system.
2. the deionized water of 5 mass parts is added, is stirred 10 minutes.
3. the shitosan of 1 mass parts and the tetraethyl orthosilicate of 56 mass parts are added, is stirred 10 minutes.
4. the ammoniacal liquor of 3 mass parts is dropwise added dropwise, adds the disodium ethylene diamine tetraacetate of 1 mass parts that 1-2 is stirred at room temperature
Individual hour.
5. adding the acetone demulsification of 80 mass parts is precipitated out nanosphere, adds 1,2 propane diols of 5 mass parts to be surpassed
Sonication.It is subsequently adding a certain amount of deionized water and ethanol is centrifuged repeatedly washing for several times.
6. the above-mentioned nano silicon of 5 mass parts is added to the deionized water of 100 mass parts and the second of 200 mass parts
In mixed alkoxide solution, it is sufficiently stirred for 10 minutes, adds the polyethylene glycol of 8 mass parts, continues to stir 10 minutes.
7. under mechanical agitation, by the metering system acid oxidase hydroxypropyl methyl dimethoxysilane of 2 mass parts dropwise
It is added in above-mentioned solution, fully reaction 20 minutes.
8. the stannous chloride of 1 mass parts is added in above-mentioned solution, be sufficiently stirred for 8 minutes, then by the first of 6 mass parts
Base Glycidyl Acrylate is added in above-mentioned solution, is stirred 30 minutes.
9. will be received with metering system acid oxidase hydroxypropyl methyl dimethoxysilane and GMA are modified
Rice silica centrifuge washing is multiple.
Fig. 1 is the transmission electron microscope picture of modified manometer silicon dioxide manufactured in the present embodiment.
Embodiment 2
1. by the hexamethylene of 100 mass parts, the phenethyl phenol poly-oxypropylene polyoxyethylene ether of 12 mass parts, 25 mass parts
N-hexyl alcohol, the Unigly GO 102S of 10 mass parts are well mixed, and stir 15 minutes, in microemulsion system.
2. the deionized water of 3 mass parts is added, is stirred 18 minutes.
3. the shitosan of 1 mass parts and the tetraethyl orthosilicate of 6 mass parts are added, is stirred 6 minutes.
4. the ammoniacal liquor of 2 mass parts is dropwise added dropwise, adds the disodium ethylene diamine tetraacetate of 1 mass parts to be stirred at room temperature 1
Hour.
5. adding the acetone demulsification of 60 mass parts is precipitated out nanosphere, and adding 1,2 propane diols of 10 mass parts is carried out
It is ultrasonically treated.It is subsequently adding a certain amount of deionized water and ethanol is centrifuged repeatedly washing for several times.
6. the above-mentioned nano silicon of 2-8 mass parts is added to the deionized water and 200 mass parts of 100 mass parts
In alcohol mixed solution, it is sufficiently stirred for 8 minutes, adds the polyethylene glycol of 6 mass parts, continues to stir 10 minutes.
7. under mechanical agitation, by the metering system acid oxidase hydroxypropyl methyl dimethoxysilane of 1 mass parts dropwise
It is added in above-mentioned solution, fully reaction 30 minutes.
8. the stannous chloride of 1.5 mass parts is added in above-mentioned solution, be sufficiently stirred for 8 minutes, then by 6 mass parts
GMA is added in above-mentioned solution, is stirred 30 minutes.
9. will be received with metering system acid oxidase hydroxypropyl methyl dimethoxysilane and GMA are modified
Rice silica centrifuge washing is multiple.
Embodiment 3
1. by the hexamethylene of 100 mass parts, the phenethyl phenol poly-oxypropylene polyoxyethylene ether of 10 mass parts, 20 mass parts
N-hexyl alcohol, the Unigly GO 102S of 10 mass parts are well mixed, and stir 15 minutes, in microemulsion system.
2. the deionized water of 4 mass parts is added, is stirred 20 minutes.
3. the shitosan of 2 mass parts and the tetraethyl orthosilicate of 6 mass parts are added, is stirred 8 minutes.
4. the ammoniacal liquor of 2 mass parts is dropwise added dropwise, adds the disodium ethylene diamine tetraacetate of 1 mass parts to be stirred at room temperature 2
Hour.
5. adding the acetone demulsification of 60 mass parts is precipitated out nanosphere, adds 1,2 propane diols of 5 mass parts to be surpassed
Sonication.It is subsequently adding a certain amount of deionized water and ethanol is centrifuged repeatedly washing for several times.
6. the above-mentioned nano silicon of 8 mass parts is added to the deionized water of 100 mass parts and the second of 200 mass parts
In mixed alkoxide solution, it is sufficiently stirred for 10 minutes, adds the polyethylene glycol of 5 mass parts, continues to stir 10 minutes.
7. under mechanical agitation, by the metering system acid oxidase hydroxypropyl methyl dimethoxysilane of 2 mass parts dropwise
It is added in above-mentioned solution, fully reaction 10-30 minutes.
8. the stannous chloride of 2 mass parts is added in above-mentioned solution, be sufficiently stirred for 5 minutes, then by the first of 6 mass parts
Base Glycidyl Acrylate is added in above-mentioned solution, is stirred 35 minutes.
9. will be received with metering system acid oxidase hydroxypropyl methyl dimethoxysilane and GMA are modified
Rice silica centrifuge washing is multiple.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or uses the present invention.
Various modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The scope most wide for causing.
Claims (2)
1. a kind of preparation method of modified manometer silicon dioxide, it is characterised in that comprise the following steps：
Step a) is by 100-120 mass parts hexamethylene, 10-20 mass parts phenethyl phenol poly-oxypropylene polyoxyethylene ether, 20-30 matter
Amount part n-hexyl alcohol and the mixing of 10-15 mass parts Unigly GO 102S, obtain microemulsion system after stirring, mixing time is 10-15
Minute；
Step b) is successively to addition deionized water, 1-2 mass parts shitosan and the positive silicic acid of 2-6 mass parts in the microemulsion system
Ethyl ester, stirring is dropwise added dropwise 1-3 mass parts ammoniacal liquor, adds 1-2 mass parts disodium ethylene diamine tetraacetates, and 50-80 is added after stirring
Mass parts acetone, is subsequently adding the propane diols of 5-10 mass parts 1,2 and deionized water is washed, and obtains nano silicon；
Step c) adds into deionized water and alcohol mixed solution the nano silicon that 2-8 mass parts steps b is obtained, and stirs
The polyethylene glycol of 5-8 mass parts is added after mixing, continues to stir, the metering system acid oxidase hydroxypropyl methyl two of 1-2 mass parts is added dropwise
Methoxy silane, obtains mixed solution after reaction；
The stannous chloride of 1-2 mass parts is added in the mixed solution that step d) is obtained to step c, 5-10 mass parts are added after stirring
GMA, modified manometer silicon dioxide is obtained after reaction.
2. preparation method according to claim 1, it is characterised in that in step c), the deionized water is 100 mass
Part, ethanol is 200 mass parts.
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