CN104275213B - There is the preparation method of the amine bridging organic silicon nano spherical particles of hydrophobic performance - Google Patents
There is the preparation method of the amine bridging organic silicon nano spherical particles of hydrophobic performance Download PDFInfo
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- CN104275213B CN104275213B CN201310284651.3A CN201310284651A CN104275213B CN 104275213 B CN104275213 B CN 104275213B CN 201310284651 A CN201310284651 A CN 201310284651A CN 104275213 B CN104275213 B CN 104275213B
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Abstract
The present invention relates to the preparation method of a kind of amine bridging organic silicon nano spherical particles with hydrophobic performance.This spherical particles is a kind of amine bridging organosilicon containing organic group.This amine bridging organic silicon nano spherical particles has hydrophobicity, and water droplet contact angle is between 95 170 °, and has the strongest adhesion to noble metal nano particles, is with a wide range of applications at catalytic field as catalyst carrier.The method is simple to operate, and raw material is easy to get, low cost.
Description
Technical field
The present invention relates to the system of a kind of amine bridging organic silicon nano spherical particles (AOS) with hydrophobic performance
Preparation Method.
Background technology
The organic silicon nano spherical particles with hydrophobic performance is wide in catalytic field application as catalyst carrier
General, cause the extensive concern of Chinese scholars.In hydrocarbon compound oxidizing process, on the one hand, the end
Thing has the character of oleophilic drainage, and because there being a lot of hydroxyl to have hydrophilic property on used catalyst carrier surface
Matter so that substrate is difficult to close to catalyst, causes substrate conversion efficiency low；On the other hand, hydrocarbon oxidation process
Middle meeting is with the generation of water, and the water of generation is more easy to adsorb in active sites, causes catalysqt deactivation.Have thin
The catalyst carrier of aqueous nature has following both sides advantage, one, catalyst hydrophobic oleophilic oil, be more easy to
Substrate is close；Its two, during hydrocarbon oxidation with generate water, can be desorbed in time, meanwhile, generation
Oxidation product is also easier to be desorbed from catalyst surface, it is to avoid deep oxidation, thus improves the choosing of target product
Selecting property.The introducing of metal active position, especially noble metal, have higher requirement to carrier.Because it is golden
If belonging to and not having certain to interact between carrier, following both sides problem can be caused: (1) metal is difficult and inhales
It is attached on carrier；(2) in application process, adsorbed metal easily runs off and inactivates.Drawing of nitrogen element
Enter, the effect of rivet can be played, have stronger active force between noble metal and nitrogen so that noble metal is easy
Absorption is on carrier, and can avoid loss in use.In work before us, built
Found the nano combined oxygen of Double-functionalized mesopore silicon oxide material (CN200610114401.5), organic decoration
Compound material (CN200810011655.3), adhesive type hydrophobic material (CN201010521305.9), double
The preparation method of function hollow nanocomposite oxide material (CN201010521321.8), the mesh of the present invention
The preparation method being to provide a kind of nitrogenous organic silicon nano spherical particles with hydrophobic performance.The method is grasped
Making simple, raw material is easy to get, low cost.
Summary of the invention
The present invention provides a kind of amine bridging organic silicon nano spherical particles with hydrophobic performance and preparation side thereof
Method.
The preparation process of the described amine bridging organic silicon nano spherical particles with hydrophobic performance, can be by following behaviour
Make:
A) inorganic precipitant dispersion in oil phase and homogeneous precipitation thereof: surfactant, organic facies, helps table
Face activating agent and ammonia are configured to solution A according to a certain percentage.Double (trimethoxy is silica-based) propylamine or double (three
Methoxyl group is silica-based) ethylenediamine and organosilan be silicon source, wiring solution-forming B.Under room temperature, solution B is instilled micro-
In latex A, stir 1-48h.
The mass ratio of the final mixed solution of gained is 1-10 surfactant: 0.5-6 ammonia: 5-15 is organic
Phase: 0-6 cosurfactant: 1 pair of (trimethoxy is silica-based) propylamine or double (trimethoxy is silica-based) second
Diamidogen: 0.05-1.5 organosilan；Ammonia concn is 1-30wt%.
Add the acetone breakdown of emulsion of 1-15 times of silicon source quality, be centrifuged and obtain solid, add 4-60 times of silicon source quality
Alcohol reflux 5-60min, centrifugal, repeats 2-5 time and washs.
Described surfactant is the C8-20 sodium n-alkylbenzenesulfonate in anion surfactant or α-alkene
Base sodium sulfonate, or be the organic primary amine of C8-20 long-chain in nonionic surfactant, Np series or tween
Series of surfactants, or be the CTAB in cationic surfactant.
Described organic facies is hexamethylene, normal hexane or toluene.
Described cosurfactant is n-butyl alcohol, n-amyl alcohol, hexanol or n-octyl alcohol.
Described organosilan is: MTMS, ethyl trimethoxy silane, propyl trimethoxy
Silane, r-chloropropyl trimethoxyl silane, vinyltrimethoxy silane, phenyltrimethoxysila,e, 12
Alkyl trimethoxysilane, octadecyl trimethoxysilane, trifluoro propyl trimethoxy silane, perfluor certain herbaceous plants with big flowers
One or more in base trimethoxy silane and pentafluorophenyl group trimethoxy silane.
The molecular structure of double (trimethoxy is silica-based) propylamine is as follows:
The molecular structure of double (trimethoxy is silica-based) ethylenediamine is as follows:
Prepared by the present invention has the nitrogenous organic silicon nano spherical particles of hydrophobic performance, and size is controlled, particle diameter
Fig. 1 and Fig. 2 is seen) at 20-1000nm(.Prepared surface has hydrophobic property, and water droplet contact angle is 95-170
° (see the built-in figure of Fig. 1).The prepared nitrogenous easy ADSORPTION OF GOLD of organic silicon nano spherical particles with hydrophobic performance
Metal nano-particle (see figure 3).
This amine bridging organic silicon nano spherical particles has a hydrophobic property, and hydrophobic performance is controlled, the containing of nitrogen
Measure the most controlled.
The present invention regulates and controls hydrophobicity by the amount controlling organosilicon source, it is possible to obtain hydrophobic silicone nanosphere
Type granule, contact angle is between 95-170 °.
Precipitant is water miscible, and silane is oil-soluble, in order to synthesize uniform particle diameter, and the tool of high dispersive
There is the nitrogenous organic silicon nano spherical particles of hydrophobic performance, it is necessary to make precipitant and silane fully and uniform contact,
The present invention uses surfactant and cosurfactant by ammonia spirit high dispersive among oil phase so that silicon
Alkane and precipitant are fully and uniform contact, homogeneous precipitation.Can be at matrix by simple deposition and burin-in process
One super hydrophobic surface of upper formation.
Accompanying drawing explanation
The organic silicon nano spherical particles K(Ph-AOS of the phenyl modification amine bridging of synthesis in Fig. 1 example 3)
Transmission electron microscope photo.
The organic silicon nano spherical particles K(Ph-AOS of phenyl modification amine bridging in Fig. 2 example 3) size
Distribution.
The organic silicon nano spherical particles K(Ph-AOS of phenyl modification amine bridging in Fig. 3 example 3) Pt is received
The absorption of rice corpuscles.
The organic silicon nano spherical particles K(Ph-AOS of phenyl modification amine bridging in Fig. 4 example 3) Infrared Characterization
Figure.
Detailed description of the invention
Surfactant, organic facies, cosurfactant and ammonia are configured to solution A according to a certain percentage.One
Quantitative double (trimethoxy is silica-based) propylamine or double (trimethoxy is silica-based) ethylenediamine and organosilan are made into
Solution B.
Under room temperature, solution B is instilled in microemulsion A, stir 1-48h.The quality of the final mixed solution of gained
Ratio is 1-10 surfactant: 0.5-6 ammonia: 5-15 organic facies: 0-6 cosurfactant: 1 pair (three
Methoxyl group is silica-based) propylamine or double (trimethoxy is silica-based) ethylenediamine: 0.05-1.5 organosilan.Add 1-15
The acetone breakdown of emulsion of times silicon source quality, centrifugal obtains solid, adds the alcohol reflux 5-60 of 4-60 times of silicon source quality
Min, centrifugal, repeat 2-5 washing, 80 ° of C are dried 12h.
The method provided the present invention below by embodiment is described in detail, but limits this most in any form
Bright.
Embodiment 1: methyl modify amine bridging organic silicon nano spherical particles A(Me-AOS) preparation
Take 6.0g myristyl benzene sulfonic acid sodium salt, 15.0g toluene, 2.0g n-amyl alcohol and 3.0g15wt%
Ammonia mixes to obtain microemulsion A；Double (trimethoxy the is silica-based) propylamine of 1.0g and 0.6g methyl trimethoxy epoxide silicon
Alkane is solution B.Under agitation solution B is instilled in solution A, aging 10h；It is subsequently adding 12g acetone,
Stirring 30min, is centrifuged and obtains solid.
In this solid, add 50g ethanol, heated and stirred 30min, be centrifuged；Repeat this step 4 time, directly
Clean to removal of surfactant.
Embodiment 2: the preparation of the organic silicon nano spherical particles B-J of organic decoration amine bridging
The same A of preparation method of the organic silicon nano spherical particles B-J of organic decoration amine bridging, difference is
The kind of organosilan and addition, the concrete organosilan kind used and addition are shown in Table 1, obtained
Material is listed in table 1.
The kind of the organosilan used in the organic silicon nano spherical particles B-J preparation of table 1 organic decoration amine bridging
And addition
Embodiment 3: the organic silicon nano spherical particles K(Ph-AOS of phenyl modification amine bridging) preparation
Take 2.0g Np-12,6.0g hexamethylene, 6.0g n-octyl alcohol and 5.0g10wt% ammonia, obtain molten
Liquid A；Double (trimethoxy is silica-based) ethylenediamine 1.0g phenyltrimethoxysila,e of 1.0g is solution B；?
Under stirring, solution B is added in solution A, aging 24h；Then, add 5g acetone, stir 30min,
It is centrifuged and obtains solid.
In this solid, add 30g ethanol, heated and stirred 10min, be centrifuged；Repeat this step 5 time, directly
Clean to removal of surfactant；Gained solid is dispersed in 10g ethanol.As depicted in figs. 1 and 2,
Can be seen that the organic silicon nano spherical particles of phenyl modification amine bridging, uniform particle sizes, particle diameter is at 90nm, table
Face is the most coarse, and water droplet contact angle is 150 °.Infrared Characterization (Fig. 3): 3074,3050cm-1, for benzene
Base group C-H stretching vibration peak, 744,698cm-1For single-substituted ring vibration peak, 2930,2883,
1460 and 1414cm-1For bridging fatty carbon chain C-H vibration peak, 1119cm-1For Si-C absworption peak, 1032
cm-1Absworption peak for Si-O-Si skeleton.Infrared Characterization explanation is successfully prepared for the amine bridging of phenyl modification
Organic silicon nano spherical particles.
Embodiment 4: the preparation of the organic silicon nano spherical particles L-R of organic decoration amine bridging
The same K of preparation method of the organic silicon nano spherical particles L-R of organic decoration amine bridging, difference is
In the kind of organosilan and addition, kind and the addition of the concrete organosilan used are shown in Table 2, gained
To material be listed in table 2.
The organosilan used in the organic silicon nano spherical particles L-R preparation of table 2 organic decoration amine bridging
Kind and addition
| Material number | Organosilan | Organosilan addition (g) | Title material |
| L | Phenyltrimethoxysila,e | 0.2 | Ph-AOS |
| M | Phenyltrimethoxysila,e | 0.4 | Ph-AOS |
| N | Phenyltrimethoxysila,e | 0.8 | Ph-AOS |
| O | Pentafluorophenyl group trimethoxy silane | 0.1 | Fph-AOS |
| P | Pentafluorophenyl group trimethoxy silane | 0.5 | Fph-AOS |
| Q | Perfluor certain herbaceous plants with big flowers base trimethoxy silane | 0.3 | PFO-AOS |
| R | Perfluor certain herbaceous plants with big flowers base trimethoxy silane | 1.5 | PFO-AOS |
Embodiment 5: the organic silicon nano spherical particles S(Do-AOS of organic decoration amine bridging) preparation
Take 9.0g CTAB, 10.0g normal hexane, 4.0g hexanol and 1.0g5
Wt% ammonia mixes to obtain microemulsion liquid A；Double (trimethoxy the is silica-based) propylamine of 1.0g and 0.1g dodecyl
Trimethoxy silane is solution B；Under agitation solution B is instilled in solution A, aging 45h；Then,
Add 15g acetone, stir 30min, be centrifuged and obtain solid.
In this solid, add 10g ethanol, heated and stirred 50min, be centrifuged；Repeat this step 3 time, directly
Clean to removal of surfactant.
The preparation of the organic silicon nano spherical particles T-Z of embodiment 6 organic decoration amine bridging
The same S of preparation method of the organic silicon nano spherical particles T-Z of organic decoration amine bridging, difference is
The kind of organosilan and addition, the concrete organosilan used and addition kind are shown in Table 3, obtained
Material is listed in table 3.
The organosilan used in the organic silicon nano spherical particles T-Z preparation of table 3 organic decoration amine bridging
Kind and addition
The amine bridging organic silicon nano spherical particles with hydrophobic performance prepared by the method that the present invention provides, is a kind of
Amine bridging organosilicon containing organic group.This amine bridging organic silicon nano spherical particles has hydrophobicity, and right
Noble metal nano particles has the strongest adhesion, as catalyst carrier before catalytic field has a wide range of applications
Scape.The method is simple to operate, and raw material is easy to get, low cost.
Being dispersed in 20mL0.01g Pt nanoparticle solution by 0.1g material K, Pt nanoparticle is complete
Being adsorbed onto material L business, after being centrifuged, solution is clarified, as shown in Figure 4.
Claims (4)
1. there is the preparation method of the amine bridging organic silicon nano spherical particles of hydrophobic performance, it is characterised in that:
Inorganic precipitant disperses and homogeneous precipitation in oil phase: surfactant, organic facies, cosurfactant and precipitant ammonia are proportionally configured to microemulsion A；Double (trimethoxy is silica-based) propylamine or double (trimethoxy is silica-based) ethylenediamine and organosilan are collectively as silicon source, wiring solution-forming B；Under room temperature, solution B is instilled in microemulsion A, stir 1-48h, obtain final mixed solution；
Add the acetone breakdown of emulsion of 1-15 times of silicon source quality, be centrifuged and obtain solid；
Add the alcohol reflux 5-60min of 4-60 times of silicon source quality, centrifugal；Repeat alcohol reflux and centrifugal process 2-5 time, obtain product；
The mass ratio of the final mixed solution of gained is, 1-10 surfactant: 0.5-6 ammonia: 5-15 organic facies: 1-6 cosurfactant: 1 pair of (trimethoxy is silica-based) propylamine or double (trimethoxy is silica-based) ethylenediamine: 0.05-1.5 organosilan；
Ammonia concn is 1-30wt%；
Described surfactant is the C8-20 sodium n-alkylbenzenesulfonate in anion surfactant or α-sodium olefin sulfonate, or be the organic primary amine of C8-20 long-chain in nonionic surfactant, Np series or TWEEN Series surfactant, or it is the cetyl trimethylammonium bromide in cationic surfactant；
Described organic facies is hexamethylene, normal hexane or toluene；
Cosurfactant is n-butyl alcohol, n-amyl alcohol, hexanol or n-octyl alcohol.
2. according to the preparation method described in claim 1, it is characterised in that: described organosilan is: one or two or more kinds in MTMS, ethyl trimethoxy silane, propyl trimethoxy silicane, r-chloropropyl trimethoxyl silane, vinyltrimethoxy silane, phenyltrimethoxysila,e, dodecyltrimethoxysilane, octadecyl trimethoxysilane, trifluoro propyl trimethoxy silane, perfluor certain herbaceous plants with big flowers base trimethoxy silane and pentafluorophenyl group trimethoxy silane.
3. according to the preparation method described in claim 1, it is characterised in that: organosilan is 0.1-70% with the mass ratio in silicon source.
4. according to the preparation method described in claim 1, it is characterised in that: it is 20-1000nm that product has the nitrogenous organic silicon nano spherical particles particle diameter of hydrophobic performance；Water droplet contact angle is 95-170 °.
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| CN103113763A (en) * | 2013-02-26 | 2013-05-22 | 南京大学南通材料工程技术研究院 | Method for modifying clay by using organic silicon micro-emulsion |
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| CN103113763A (en) * | 2013-02-26 | 2013-05-22 | 南京大学南通材料工程技术研究院 | Method for modifying clay by using organic silicon micro-emulsion |
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