CN108531292A - Preparing spherical SiO 2 nanometer fragrance of light-operated sustained release and preparation method thereof - Google Patents
Preparing spherical SiO 2 nanometer fragrance of light-operated sustained release and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/141—Preparation of hydrosols or aqueous dispersions
- C01B33/1412—Preparation of hydrosols or aqueous dispersions by oxidation of silicon in basic medium
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- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/141—Preparation of hydrosols or aqueous dispersions
- C01B33/1415—Preparation of hydrosols or aqueous dispersions by suspending finely divided silica in water
- C01B33/1417—Preparation of hydrosols or aqueous dispersions by suspending finely divided silica in water an aqueous dispersion being obtained
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0003—Compounds of unspecified constitution defined by the chemical reaction for their preparation
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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Abstract
A kind of preparing spherical SiO 2 nanometer fragrance of light-operated sustained release and preparation method thereof, the preparation method includes：Synthesize photosensitive silane coupling agent；Prepare mesoporous nano silicon dioxide ball；Photosensitive nanoparticle mesoporous silica spheres are obtained by the reaction in photosensitive silane coupling agent and mesoporous nano silicon dioxide ball；By photosensitive nanoparticle mesoporous silica spheres carried perfume, the preparing spherical SiO 2 nanometer fragrance of light-operated sustained release is obtained after removing the fragrance of organic solvent and unentrapped.The present invention contains fragrance using mesoporous nano silicon dioxide and the nanometer fragrance for being prepared for light-operated sustained release solves the problems, such as that the unstable, volatile of fragrance, fragrance discharge the uncontrollable of process.
Description
Technical field
The invention belongs to technical field of fine, and in particular to a kind of preparing spherical SiO 2 nanometer fragrance of light-operated sustained release
And preparation method thereof.
Background technology
As the smell of the raising fragrance of progress people's quality of the life of social civilization is gradually praised highly by people.Fragrance is
It is widely used in the fields such as cosmetics silk, leather and wallpaper.But fragrance be mainly volatile small molecule chemical composition not
It is stable, volatile.The major reason of fragrance long-term effect difference is the uncontrollable of fragrance release process, and therefore, it is necessary to controllable precises
Fragrance is discharged to solve existing technical problem.
Invention content
In view of the deficiencies of the prior art, the main purpose of the present invention is to provide a kind of preparing spherical SiO 2s of light-operated sustained release
Nanometer fragrance and preparation method thereof, at least one of to solve the above problems.
To achieve the goals above, as one aspect of the present invention, a kind of spherical titanium dioxide of light-operated sustained release is provided
The preparation method of silicon nanometer fragrance, includes the following steps：
(1) 3- isocyanate group propyl trimethoxy silicane and 4- aminoazabenzol heating reflux reactions are obtained into photosensitive silicon
Alkane coupling agent；
(2) cetyl trimethylammonium bromide and ammonia spirit are dissolved in heating in deionized water and obtain colloidal sol, 0.5~2h
It is added to after tetraethyl orthosilicate is diluted afterwards in the colloidal sol, 30~80 DEG C are obtained by the reaction mesoporous nano silicon dioxide ball；
(3) photosensitive silane coupling agent that step (1) obtains and the mesoporous nano silicon dioxide ball that step (2) obtains are reacted
Obtain photosensitive nanoparticle mesoporous silica spheres；
(4) the photosensitive nanoparticle mesoporous silica spheres carried perfume for obtaining step (3) removes organic solvent and unentrapped
Fragrance after obtain the preparing spherical SiO 2 nanometer fragrance of light-operated sustained release.
Preferably, in step (1), 3- isocyanate group propyl trimethoxy silicane and the mass ratio of 4- aminoazabenzols are
1~5: 1.
Preferably, in step (1), the method for purification of the photosensitive silane coupling agent be by crude product -20 DEG C just oneself
It is recrystallized in alkane.
Preferably, in step (2), the grain size of the mesoporous nano silicon dioxide ball is 50~150nm.
Preferably, in step (2), tetraethyl orthosilicate dilutes solvent for use and is selected from ethyl alcohol, methanol, n-hexane or tetrahydrochysene furan
It mutters.
Preferably, in step (2), the processing method of the reaction solution is：Filter residue is obtained by filtration, first with 95% ethanol solution
It is fully washed with deionized water, solid filter residue is distributed in the ethanol solution containing 0.01M hydrochloric acid after filtering and is heated to 60
DEG C, it filters to take filter residue and is fully washed with deionized water with 95% ethanol solution again, then calcining removes hexadecane in Muffle furnace
Base trimethylammonium bromide.
Preferably, in step (3), the mass ratio of the mesoporous nano silicon dioxide ball and the photosensitive silane coupling agent is
1: 1~5.
Preferably, in step (4), the fragrance is the fragrance of a flower, root of Aucklandia lappa Decne or fruity；The photosensitive nanoparticle mesoporous silica spheres
Mass ratio with fragrance is 1~5: 1.
Preferably, in step (4), the fragrance of organic solvent and unentrapped, dialysis bag retention molecular weight are removed by dialysis
It is 7000, dialyzate is deionized water, is protected from light dialysis.
As another aspect of the present invention, a kind of light-operated sustained release being prepared according to preparation method above-mentioned is provided
Preparing spherical SiO 2 nanometer fragrance.
From above-mentioned technical proposal it is found that the preparing spherical SiO 2 nanometer fragrance of the light-operated sustained release of the present invention and its preparation side
Method has the advantages that：
(1) present invention contains fragrance using mesoporous nano silicon dioxide and is prepared for the nanometer perfume of light-operated sustained release
Material solves the problems, such as that the unstable, volatile of fragrance, fragrance discharge the uncontrollable of process；
(2) fragrance load factor of the invention is high, and fragrance release is uniform, slow fragrance remaining time is long；
(3) nanometer fragrance of the invention is easy to use, preparation method simply can be widely applied to daily use chemicals, weaving, leather, wall
The every field such as paper.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of the preparing spherical SiO 2 nanometer fragrance of light-operated sustained release prepared by the embodiment of the present invention 1；
Fig. 2 is the thermogravimetric analysis figure of the preparing spherical SiO 2 nanometer fragrance of light-operated sustained release prepared by the embodiment of the present invention 1；
Fig. 3 is the fragrance response release of the preparing spherical SiO 2 nanometer fragrance of light-operated sustained release prepared by the embodiment of the present invention 1
Effect.
Specific implementation mode
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment and reference
Attached drawing, the present invention is described in further detail.
The present invention provides preparing spherical SiO 2 nanometer fragrance of a kind of light-operated sustained release and preparation method thereof, the preparation sides
Method includes the following steps：
Synthesize photosensitive silane coupling agent；
Prepare mesoporous nano silicon dioxide ball；
Photosensitive nanoparticle mesoporous silica spheres are obtained by the reaction in photosensitive silane coupling agent and mesoporous nano silicon dioxide ball；
By photosensitive nanoparticle mesoporous silica spheres carried perfume, obtained after the fragrance of removing organic solvent and unentrapped light-operated
The preparing spherical SiO 2 nanometer fragrance of sustained release.
The present invention contains fragrance using mesoporous nano silicon dioxide and is prepared for the nanometer fragrance solution of light-operated sustained release
Determined fragrance unstable, volatile, fragrance release process uncontrollable problem.
Specifically, the invention discloses a kind of preparation methods of the preparing spherical SiO 2 nanometer fragrance of light-operated sustained release, including
Following steps：
(1) 3- isocyanate group propyl trimethoxy silicane and 4- aminoazabenzol heating reflux reactions are obtained into photosensitive silicon
Alkane coupling agent；
(2) cetyl trimethylammonium bromide and ammonia spirit are dissolved in heating in deionized water and obtain colloidal sol, 0.5~2h
It is added to after tetraethyl orthosilicate is diluted afterwards in the colloidal sol, 30~80 DEG C are obtained by the reaction mesoporous nano silicon dioxide ball；
(3) photosensitive silane coupling agent that step (1) obtains and the mesoporous nano silicon dioxide ball that step (2) obtains are reacted
Obtain photosensitive nanoparticle mesoporous silica spheres；
(4) the photosensitive nanoparticle mesoporous silica spheres carried perfume for obtaining step (3) removes organic solvent and unentrapped
Fragrance after obtain the preparing spherical SiO 2 nanometer fragrance of light-operated sustained release.
In step (1), the mass ratio of 3- isocyanate group propyl trimethoxy silicane and 4- aminoazabenzols is 1~5: 1.
In step (1), the method for purification of the photosensitive silane coupling agent is to tie crude product again in -20 DEG C of n-hexane
It is brilliant.
In step (2), the grain size of the mesoporous nano silicon dioxide ball is 50~150nm.
In step (2), tetraethyl orthosilicate dilutes solvent for use and is selected from ethyl alcohol, methanol, n-hexane or tetrahydrofuran.
In step (2), the processing method of the reaction solution is：Filter residue is obtained by filtration, first with 95% ethanol solution and go from
Sub- water fully washs, and solid filter residue is distributed in the ethanol solution containing 0.01M hydrochloric acid after filtering and is heated to 60 DEG C, filtering
Filter residue is taken fully to be washed with deionized water with 95% ethanol solution again, then calcining removes cetyl trimethyl in Muffle furnace
Ammonium bromide.
In step (3), the mass ratio of the mesoporous nano silicon dioxide ball and the photosensitive silane coupling agent is 1: 1~5.
In step (4), the fragrance is the fragrance of a flower, root of Aucklandia lappa Decne or fruity；The photosensitive nanoparticle mesoporous silica spheres and fragrance
Mass ratio be 1~5: 1.
In step (4), by dialysis remove organic solvent and unentrapped fragrance, dialysis bag retention molecular weight 7000,
Dialyzate is deionized water, is protected from light dialysis.
The invention also discloses a kind of preparing spherical SiO 2s for the light-operated sustained release being prepared according to preparation method above-mentioned
Nanometer fragrance.
Below in conjunction with specific embodiments and the drawings to the present invention light-operated sustained release preparing spherical SiO 2 nanometer fragrance and its
Preparation method is described in further detail.
Embodiment 1
It is prepared by the following method the nanometer fragrance of light-operated sustained release in the present embodiment, specifically includes following steps：
(1) preparation of photosensitive silane coupling agent
3- isocyanate group propyl trimethoxy silicane (247.36mg) and 4- aminoazabenzols (197.24mg) are dissolved in
It is heated to reflux in super dry tetrahydrofuran and at 80 DEG C and obtains crude product for 24 hours；Crude product is recrystallized in -20 DEG C of n-hexane
To the photosensitive silane coupling agent of purifying.
(2) preparation of mesoporous nano silicon dioxide ball
Cetyl trimethylammonium bromide (400mg) and 25% ammonia spirit (7mL) are dissolved in deionized water (96mL)
In and be heated to 80 DEG C；Tetraethyl orthosilicate (1.87mL) is dissolved in ethyl alcohol (2mL) after 30min and is incited somebody to action in whipping process
It is added dropwise in above-mentioned surfactant colloidal sol；80 DEG C reaction 2h after filter residue is collected by filtration, first use 95% ethanol solution and
Deionized water is fully washed, and solid filter residue is distributed to the ethanol solution containing 0.01M hydrochloric acid after filtering, and is heated to 60 DEG C；
Filter residue is filtered to take after 6h and is fully washed with deionized water with 95% ethanol solution；Then 550 DEG C of calcining 5h are removed in Muffle furnace
Cetyl trimethylammonium bromide surfactant is gone to obtain mesoporous nano silicon dioxide ball.
(3) photosensitive nanoparticle mesoporous silica spheres are prepared
Mesoporous silica nanospheres (100mg) and photosensitive silane coupling agent (200mg) are dissolved in dry toluene
Lower 80 DEG C of nitrogen protection flows back for 24 hours in (50mL)；Filter residue is collected by filtration and washs vacuum drying with super dry toluene and obtains photosensitive receive
Rice mesoporous silica spheres.
(4) photosensitive nanoparticle mesoporous silica spheres carried perfume
Photosensitive nanoparticle mesoporous silica spheres (100mg) are dissolved in deionized water (50mL) santal 803 (80mg) is molten
Solution is in ethyl alcohol (5mL) and is added dropwise to vigorous stirring in photosensitive nanoparticle mesoporous silica spheres aqueous solution；Illumination is for 24 hours
The bag filter that the fragrance selective retention molecular weight of organic solvent and unentrapped is 7000 is removed by dialysis afterwards, dialyzate be go from
Sub- water is protected from light dialysis, finally obtains the nanometer fragrance of light-operated sustained release.
The nanometer fragrance for the light-operated sustained release that embodiment 1 is prepared using transmission electron microscope is characterized, as a result such as Fig. 1 institutes
Show, products therefrom grain size is the nanometer fragrance grain size for the light-operated sustained release that 50nm or so is synthesis.
The nanometer fragrance of the light-operated sustained release of above-mentioned gained has santal fragrance, through thermal gravimetric analysis results as shown in Fig. 2, carrying fragrant
Amount about 37.42%.
Embodiment 2
It is prepared by the following method the nanometer fragrance of light-operated sustained release in the present embodiment, specifically includes following steps：
(1) preparation of photosensitive silane coupling agent
3- isocyanate group propyl trimethoxy silicane (247.36mg) and 4- aminoazabenzols (197.24mg) are dissolved in
It is heated to reflux in super dry tetrahydrofuran and at 80 DEG C and obtains crude product for 24 hours；Crude product is recrystallized in -20 DEG C of n-hexane
To the photosensitive silane coupling agent of purifying.
(2) preparation of mesoporous nano silicon dioxide ball
Cetyl trimethylammonium bromide (400mg) and 25% ammonia spirit (7mL) are dissolved in deionized water (96mL)
In and be heated to 80 DEG C；Tetraethyl orthosilicate (1.87mL) is dissolved in methanol (2mL) and in whipping process by it after 1h
It is added dropwise in above-mentioned surfactant colloidal sol；70 DEG C reaction 2h after filter residue is collected by filtration, first with 95% ethanol solution with go
Ionized water fully washs, and solid filter residue is distributed to the ethanol solution containing 0.01M hydrochloric acid after filtering, and is heated to 60 DEG C；6h
After filter to take filter residue and fully washed with deionized water with 95% ethanol solution；Then 550 DEG C of calcining 5h in Muffle furnace, remove
Cetyl trimethylammonium bromide surfactant obtains mesoporous nano silicon dioxide ball.
(3) photosensitive nanoparticle mesoporous silica spheres are prepared
Mesoporous silica nanospheres (100mg) and photosensitive silane coupling agent (300mg) are dissolved in dry toluene
Lower 80 DEG C of nitrogen protection flows back for 24 hours in (50mL)；Filter residue is collected by filtration and washs vacuum drying with super dry toluene and obtains photosensitive receive
Rice mesoporous silica spheres.
(4) photosensitive nanoparticle mesoporous silica spheres carried perfume
Photosensitive nanoparticle mesoporous silica spheres (200mg) are dissolved in deionized water (100mL) santal 803 (80mg) is molten
Solution is in ethyl alcohol (5mL) and is added dropwise to vigorous stirring in photosensitive nanoparticle mesoporous silica spheres aqueous solution；Illumination is for 24 hours
The fragrance of organic solvent and unentrapped, the bag filter that selective retention molecular weight is 7000 are removed by dialysis afterwards, dialyzate is to go
Ionized water is protected from light the nanometer fragrance that dialysis finally obtains light-operated sustained release.
The nanometer fragrance of the light-operated sustained release of above-mentioned gained is 80nm or so through transmission electron microscope characterization grain size, carries fragrant amount and is about
36.22%.
Embodiment 3
It is prepared by the following method the nanometer fragrance of light-operated sustained release in the present embodiment, specifically includes following steps：
(1) preparation of photosensitive silane coupling agent
3- isocyanate group propyl trimethoxy silicane (247.36mg) and 4- aminoazabenzols (197.24mg) are dissolved in
In super dry tetrahydrofuran, and it is heated to reflux at 80 DEG C and obtains crude product for 24 hours；Crude product is recrystallized in -20 DEG C of n-hexane
The photosensitive silane coupling agent purified.
(2) preparation of mesoporous nano silicon dioxide ball
Cetyl trimethylammonium bromide (400mg) and 25% ammonia spirit (7mL) are dissolved in deionized water (96mL)
In and be heated to 80 DEG C；Tetraethyl orthosilicate (1.87mL) is dissolved in n-hexane (2mL) and in whipping process after 45min
It is added dropwise in above-mentioned surfactant colloidal sol；Filter residue is collected by filtration after 50 DEG C of reaction 2h, first with 95% ethanol solution
It is fully washed with deionized water, solid filter residue is distributed to the ethanol solution containing 0.01M hydrochloric acid after filtering, and be heated to 60
℃；Filter residue is filtered to take after 6h and is fully washed with deionized water with 95% ethanol solution；Then 550 DEG C of calcining 5h in Muffle furnace
It removes cetyl trimethylammonium bromide surfactant and obtains mesoporous nano silicon dioxide ball.
(3) photosensitive nanoparticle mesoporous silica spheres are prepared
Mesoporous silica nanospheres (100mg) and photosensitive silane coupling agent (100mg) are dissolved in dry toluene
Lower 80 DEG C of nitrogen protection flows back for 24 hours in (50mL)；Filter residue is collected by filtration and washs vacuum drying with super dry toluene and obtains photosensitive receive
Rice mesoporous silica spheres.
(4) photosensitive nanoparticle mesoporous silica spheres carried perfume
Photosensitive nanoparticle mesoporous silica spheres (80mg) are dissolved in deionized water (50mL), linalool (80mg) is dissolved
In ethyl alcohol (5mL), and it is added dropwise to vigorous stirring in MS-S photosensitive nanoparticle mesoporous silica spheres aqueous solutions；Illumination
Remove the fragrance of organic solvent and unentrapped, the bag filter that selective retention molecular weight is 7000 by dialysis afterwards for 24 hours, dialyzate is
Deionized water is protected from light the nanometer fragrance that dialysis finally obtains light-operated sustained release.
The nanometer fragrance of the light-operated sustained release of above-mentioned gained is 100nm or so through transmission electron microscope characterization grain size, carries fragrant amount and is about
37.23%.
Embodiment 4
It is prepared by the following method the nanometer fragrance of light-operated sustained release in the present embodiment, specifically includes following steps：
(1) preparation of photosensitive silane coupling agent
3- isocyanate group propyl trimethoxy silicane (247.36mg) and 4- aminoazabenzols (197.24mg) are dissolved in
It is heated to reflux in super dry tetrahydrofuran and at 80 DEG C and obtains crude product for 24 hours；Crude product is recrystallized in -20 DEG C of n-hexane
To the photosensitive silane coupling agent of purifying.
(2) preparation of mesoporous nano silicon dioxide ball
Cetyl trimethylammonium bromide (400mg) and 25% ammonia spirit (7mL) are dissolved in deionized water (96mL)
In and be heated to 80 DEG C；Tetraethyl orthosilicate (1.87mL) is dissolved in tetrahydrofuran (2mL) and in whipping process after 30min
It is middle to be added dropwise in above-mentioned surfactant colloidal sol；Filter residue is collected by filtration after 80 DEG C of reaction 2h and with 95% ethanol solution
It fully washs with deionized water and then filter residue is distributed to containing in 100mL ethyl alcohol and 1mL concentrated hydrochloric acids and being heated to 60 DEG C；After 6h
It filters to take filter residue and is fully washed with deionized water with 95% ethanol solution；Then 550 DEG C of calcining 5h in Muffle furnace, remove ten
Six alkyl trimethyl ammonium bromide surfactants obtain mesoporous nano silicon dioxide ball.
(3) photosensitive nanoparticle mesoporous silica spheres are prepared
Mesoporous silica nanospheres (100mg) and photosensitive silane coupling agent (200mg) are dissolved in dry toluene
Lower 80 DEG C of nitrogen protection flows back for 24 hours in (50mL)；Filter residue is collected by filtration and washs vacuum drying with super dry toluene and obtains photosensitive receive
Rice mesoporous silica spheres.
(4) photosensitive nanoparticle mesoporous silica spheres carried perfume
Photosensitive nanoparticle mesoporous silica spheres (100mg) are dissolved in deionized water (50mL) by acetic acid linalool (80mg)
It is dissolved in ethyl alcohol (5mL) and is added dropwise to vigorous stirring in photosensitive nanoparticle mesoporous silica spheres aqueous solution；Illumination
The fragrance selective retention molecular weight of organic solvent and unentrapped is removed as 7000 bag filter by dialysis afterwards for 24 hours, dialyzate is
Deionized water is protected from light dialysis, finally obtains the nanometer fragrance of light-operated sustained release.
The nanometer fragrance of the light-operated sustained release of above-mentioned gained is 52nm or so through transmission electron microscope characterization grain size, carries fragrant amount and is about
36.67%.
Application Example
Wallpaper sample (25cm2) be immersed in above-described embodiment 1 preparation light-operated sustained release nanometer flavored aqueous solution in be protected from light
It is stirred at room temperature 12h, wherein stir speed (S.S.) is 1200rpm, and 803 a concentration of 1mg/mL of santal.Subsequent wallpaper is placed in 40 in baking oven
DEG C place 1h drying.
Wallpaper after flavoring analyzes fragrance releasing effect with gas-chromatography GC-FID, and the results are shown in Figure 3,240h compared to
Individually control fragrance Cumulative release amount about 24%, the nanometer perfume systems Cumulative release amount of light-operated sustained release prepared by embodiment 1 is only
It is 7%, realizes the sustained release under odourant molecules solar radiation, solves the problems, such as the uncontrollable of fragrance release process, and fragrance is released
Put uniformly slowly, fragrance remaining time is long, with obvious effects.
It is received in conclusion the present invention contains fragrance using mesoporous nano silicon dioxide and is prepared for light-operated sustained release
Rice fragrance solves the problems, such as that the unstable, volatile of fragrance, fragrance discharge the uncontrollable of process, and fragrance load factor is high, fragrant
Gas release is uniformly, slow, fragrance remaining time is long.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical solution and advantageous effect
Explanation, it should be understood that the above is only a specific embodiment of the present invention is not intended to restrict the invention, all in this hair
Any modification, equivalent substitution, improvement and etc. done within bright spirit and principle should be included in protection scope of the present invention it
It is interior.
Claims (10)
1. a kind of preparation method of the preparing spherical SiO 2 nanometer fragrance of light-operated sustained release, which is characterized in that include the following steps：
(1) 3- isocyanate group propyl trimethoxy silicane and 4- aminoazabenzol heating reflux reactions are obtained into photosensitive silane idol
Join agent；
(2) cetyl trimethylammonium bromide and ammonia spirit are dissolved in heating in deionized water and obtain colloidal sol, it will after 0.5~2h
It is added in the colloidal sol after tetraethyl orthosilicate dilution, 30~80 DEG C are obtained by the reaction mesoporous nano silicon dioxide ball；
(3) photosensitive silane coupling agent that step (1) obtains and the mesoporous nano silicon dioxide ball that step (2) obtains are obtained by the reaction
Photosensitive nanoparticle mesoporous silica spheres；
(4) the photosensitive nanoparticle mesoporous silica spheres carried perfume for obtaining step (3) removes the perfume (or spice) of organic solvent and unentrapped
The preparing spherical SiO 2 nanometer fragrance of light-operated sustained release is obtained after material.
2. preparation method according to claim 1, which is characterized in that in step (1), 3- isocyanate group propyl trimethoxies
The mass ratio of base silane and 4- aminoazabenzols is 1~5: 1.
3. preparation method according to claim 1, which is characterized in that in step (1), the photosensitive silane coupling agent carries
Pure method is to recrystallize crude product in -20 DEG C of n-hexane.
4. preparation method according to claim 1, which is characterized in that in step (2), the mesoporous nano silicon dioxide ball
Grain size be 50~150nm.
5. preparation method according to claim 1, which is characterized in that in step (2), tetraethyl orthosilicate dilution is used molten
Agent is selected from ethyl alcohol, methanol, n-hexane or tetrahydrofuran.
6. preparation method according to claim 1, which is characterized in that in step (2), the processing method of the reaction solution
For：Filter residue is obtained by filtration, is first fully washed with deionized water with 95% ethanol solution, after filtering by solid filter residue be distributed to containing
It in the ethanol solution of 0.01M hydrochloric acid and is heated to 60 DEG C, filters to take filter residue and fully washed with deionized water with 95% ethanol solution again
It washs, then calcining removes cetyl trimethylammonium bromide in Muffle furnace.
7. preparation method according to claim 1, which is characterized in that in step (3), the mesoporous nano silicon dioxide ball
Mass ratio with the photosensitive silane coupling agent is 1: 1~5.
8. preparation method according to claim 1, which is characterized in that in step (4), the fragrance be the fragrance of a flower, root of Aucklandia lappa Decne or
Fruity；The mass ratio of the photosensitive nanoparticle mesoporous silica spheres and fragrance is 1~5: 1.
9. preparation method according to claim 1, which is characterized in that in step (4), by dialysis remove organic solvent and
The fragrance of unentrapped, dialysis bag retention molecular weight 7000, dialyzate are deionized water, are protected from light dialysis.
10. the preparing spherical SiO 2 for the light-operated sustained release that the preparation method according to claim 1 to 9 any one is prepared
Nanometer fragrance.
Priority Applications (1)
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109504537A (en) * | 2018-11-05 | 2019-03-22 | 中国科学院过程工程研究所 | Mesoporous silicon dioxide nano fragrance of temperature control sustained-release and preparation method thereof |
| CN110205110A (en) * | 2019-05-05 | 2019-09-06 | 厦门大学 | Duct confinement-shell isolated duplicate protection perovskite nanoparticle preparation method |
| CN110358629A (en) * | 2019-06-28 | 2019-10-22 | 浙江大学 | A kind of load perfume (or spice) nanoparticle and preparation method thereof with photothermal response controlled release ability |
| CN110713191A (en) * | 2019-06-28 | 2020-01-21 | 浙江大学 | Pre-fragrant silicon dioxide nano particle and preparation method thereof |
| CN111296425A (en) * | 2020-03-31 | 2020-06-19 | 陕西地建土地工程技术研究院有限责任公司 | Preparation method of light-operated pesticide release control agent and light-operated pesticide release control agent |
| CN114455592A (en) * | 2020-11-10 | 2022-05-10 | 中国科学院过程工程研究所 | S-triazinyl modified hollow mesoporous silica and its preparation method and use |
| CN114468353A (en) * | 2022-03-01 | 2022-05-13 | 湖北中烟工业有限责任公司 | Thermosensitive response essence slow-release microcapsule and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121519A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院理化技术研究所 | Hollow silicon dioxide sub-micron sphere with inner core and its preparation method and use |
| CN102666382A (en) * | 2009-12-21 | 2012-09-12 | 花王株式会社 | Method for producing composite silica particles |
| CN103747771A (en) * | 2011-08-10 | 2014-04-23 | 宝洁公司 | Encapsulates |
| CN107416850A (en) * | 2017-09-14 | 2017-12-01 | 陕西学前师范学院 | A kind of preparation method of mesoporous hollow silica |
-
2018
- 2018-04-19 CN CN201810357621.3A patent/CN108531292B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121519A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院理化技术研究所 | Hollow silicon dioxide sub-micron sphere with inner core and its preparation method and use |
| CN102666382A (en) * | 2009-12-21 | 2012-09-12 | 花王株式会社 | Method for producing composite silica particles |
| CN103747771A (en) * | 2011-08-10 | 2014-04-23 | 宝洁公司 | Encapsulates |
| CN107416850A (en) * | 2017-09-14 | 2017-12-01 | 陕西学前师范学院 | A kind of preparation method of mesoporous hollow silica |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109504537A (en) * | 2018-11-05 | 2019-03-22 | 中国科学院过程工程研究所 | Mesoporous silicon dioxide nano fragrance of temperature control sustained-release and preparation method thereof |
| CN110205110A (en) * | 2019-05-05 | 2019-09-06 | 厦门大学 | Duct confinement-shell isolated duplicate protection perovskite nanoparticle preparation method |
| CN110205110B (en) * | 2019-05-05 | 2020-07-10 | 厦门大学 | Preparation method of pore confinement-shell isolation double-protection perovskite nano particles |
| CN110358629A (en) * | 2019-06-28 | 2019-10-22 | 浙江大学 | A kind of load perfume (or spice) nanoparticle and preparation method thereof with photothermal response controlled release ability |
| CN110713191A (en) * | 2019-06-28 | 2020-01-21 | 浙江大学 | Pre-fragrant silicon dioxide nano particle and preparation method thereof |
| CN110358629B (en) * | 2019-06-28 | 2021-05-04 | 浙江大学 | Aroma-carrying nano particle with photo-thermal response controlled release capability and preparation method thereof |
| CN111296425A (en) * | 2020-03-31 | 2020-06-19 | 陕西地建土地工程技术研究院有限责任公司 | Preparation method of light-operated pesticide release control agent and light-operated pesticide release control agent |
| CN114455592A (en) * | 2020-11-10 | 2022-05-10 | 中国科学院过程工程研究所 | S-triazinyl modified hollow mesoporous silica and its preparation method and use |
| CN114455592B (en) * | 2020-11-10 | 2023-10-20 | 中国科学院过程工程研究所 | Hollow mesoporous silica modified by sym-triazinyl, and preparation method and application thereof |
| CN114468353A (en) * | 2022-03-01 | 2022-05-13 | 湖北中烟工业有限责任公司 | Thermosensitive response essence slow-release microcapsule and preparation method and application thereof |
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| CN108531292B (en) | 2020-10-16 |
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