CN104226275A - Hollow microsphere based on methacrylic acyloxy cage-like silsesquioxane and preparation method and application thereof - Google Patents
Hollow microsphere based on methacrylic acyloxy cage-like silsesquioxane and preparation method and application thereof Download PDFInfo
- Publication number
- CN104226275A CN104226275A CN201410416125.2A CN201410416125A CN104226275A CN 104226275 A CN104226275 A CN 104226275A CN 201410416125 A CN201410416125 A CN 201410416125A CN 104226275 A CN104226275 A CN 104226275A
- Authority
- CN
- China
- Prior art keywords
- preparation
- cage
- emulsion
- methacryloxy
- poss
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention belongs to the technical field of organic and inorganic nano hybrid materials, and discloses a hollow microsphere based on methacrylic acyloxy cage-like silsesquioxane as well as a preparation method and an application thereof. The method comprises the following steps: preparing emulsion with stable methacrylic acyloxy cage-like silsesquioxane and Pickering effect, and drying the emulsion; soaking the dried emulsion by adopting a mixed solution which contains acetone and cyclohexane and serves as an etching agent so as to remove polystyrene nuclear to obtain a product. The product is extremely good in adsorption performance and can be applied to the field of sewage treatment. The operation technology is relatively simple, and experiment conditions are mild; the selected raw materials and reagents are easily obtained, and the yield of reaction is high.
Description
Technical field
The invention belongs to the technical field of organosilicon/inorganic nano-hybrid material, particularly one is based on the microballoon with hollow structure and its preparation method and application of methacryloxy cage-type silsesquioxane (MA-POSS).
Background technology
Cage-type silsesquioxane (POSS) is called polyhedral silsesquioxane again, is the general name that a class has the silsesquioxane of similar lantern structure.According to the number of silicon atoms number in POSS, again respectively referred to as T
8-POSS ([RSiO
1.5]
8), T
10-POSS ([RSiO
1.5]
10) and T
12-POSS ([RSiO
1.5]
12).Prior art has synthesized high yield pulp1, highly purified T
8-MA-POSS and T
10-MA-POSS, i.e. methacryloxy cage-type silsesquioxane, and have related article to report, as article (J.Peng, K.Xu, the H.L.Cai and J.C.Wu of J.Peng etc., RSC.Advances., 2014,4,7124-7131) and the crystallization of patent CN103214509A-cube prestox acryloxypropyl silsesquioxane and preparation method thereof.
Pickering emulsion refers to and replaces traditional chemical emulsifier with solids and the stable emulsion obtained.Solids form thin film at oil-water interfaces, thus have blocked the gathering between drop, obtained stable oil/water dispersion.Namely the emulsion with Pickering effect that patent 201410128992.6-methacryloxy cage-type silsesquioxane is stable and preparation thereof provide the stable preparation method with the emulsion of Pickering effect of a kind of methacryloxy cage-type silsesquioxane (MA-POSS).
Hollow structure material has low-density, high-specific surface area, can hold the features such as guest molecule is widely used in the fields such as environmental protection, biological medicine, electronics.Some has hydrophily or the molecular hollow structure material of hydrophobic grain, effectively can adsorb and have hydrophily or hydrophobic material, thus can be used for the aspects such as sewage disposal.The method preparing hollow polymer reported has 3 kinds: self-assembly method, template and emulsion polymerization.The preparation method of a CN102733000A-hollow polymer nanofiber of Chinese Academy Of Sciences Process Engineering Research Institute reports a kind of hollow structure material prepared by polymer nanofiber.The slow-released carrier with nanostructured that the CN1413735-of China Science & Technology University is used for medicine reports a kind of preparation with the hollow structure microballoon of excellent absorption property and sustained release performance.Although so, the monomer scope for the preparation of hollow structure microballoon is still narrower, cage-type silsesquioxane is applied to the preparation unmanned report especially of hollow structure material.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is a kind of method providing hollow microsphere prepared by methacryloxy cage-type silsesquioxane (MA-POSS).First this preparation method replaces conventional emulsifier to prepare the emulsion with Pickering effect with MA-POSS part, and then prepares a kind of hollow structure material based on MA-POSS of novelty by solvent etched.
Another object of the present invention is to the hollow microsphere based on methacryloxy cage-type silsesquioxane (MA-POSS) providing said method to prepare.
Another object of the present invention is to provide the above-mentioned application of hollow microsphere in sewage treatment area based on methacryloxy cage-type silsesquioxane (MA-POSS).Present invention demonstrates that it has good adsorptivity.
Object of the present invention is realized by following proposal:
A kind of preparation method based on the hollow microsphere of methacryloxy cage-type silsesquioxane (MA-POSS), according to following operating procedure:
(1) emulsion with Pickering effect that methacryloxy cage-type silsesquioxane is stable is prepared, dry, for subsequent use;
(2) adopt the mixed solution of acetone and cyclohexane as etching agent, soak to remove polystyrene core to dried above-mentioned emulsion, filter, obtain the hollow microsphere based on methacryloxy cage-type silsesquioxane.
Step (1) described drying is boulton process and freeze-drying.
The temperature of described boulton process is 60 DEG C, and drying time is 24 hours; Described freeze-drying temperature is-55 ~-57 DEG C, and cooling time is 24 hours.
The volume ratio of step (2) described acetone and cyclohexane is 3:7 ~ 7:3.Content of acetone is high, then etch required time long, content of acetone is low, then etch required time short.
Step (2) described immersion is at room temperature carried out, and soak time is 12 ~ 24h.
The preparation of step (1) described emulsion is according to following steps: utilize methacryloxy cage-type silsesquioxane and copolymerization monomer styrene (St) under emulsifying agent effect, in aqueous systems, emulsion reaction obtains pre-emulsion, again by seed emulsion polymerization, under initator effect, polymerisation obtains the emulsion with Pickering effect.
The amount of described methacryloxy cage-type silsesquioxane is 10 ~ 30% of copolymerization monomer styrene quality, and with the change of MA-POSS consumption, then the shell of gained hollow structure material is thick also changes thereupon;
Described methacryloxy cage-type silsesquioxane is that the compound with following structure (is respectively T
8-MA-POSS and T
10-MA-POSS):
Wherein
The hollow microsphere based on methacryloxy cage-type silsesquioxane that said method prepares.
The application of the above-mentioned hollow microsphere based on methacryloxy cage-type silsesquioxane in sewage treatment area.
The hollow structure material based on MA-POSS that said method prepares has uniform hollow structure and good absorption property.And having in the preparation process of the emulsion of Pickering effect, MA-POSS serves the effect replacing conventional emulsifier, thus effectively reduces the use of emulsifying agent.Because MA-POSS has organic-inorganic nano hybrid structure, and molecular weight is comparatively large, and it has good hot property, mechanical performance, thus also substantially increases the performance of hollow structure material.
The T that the present invention is used
8-MA-POSS and T
10-MA-POSS prepares with reference to the method for (J.Peng, K.Xu, H.L.Cai and J.C.Wu, RSC.Advances., 2014,4,7124-7131) document.
The T that the present invention is used
8-MA-POSS and T
10the method that-MA-POSS and St reacts emulsion reference patent application CN103923248A-methacryloxy cage-type silsesquioxane of the gained stable emulsion and preparation thereof with Pickering effect prepares.
Mechanism of the present invention is:
First the present invention utilizes MA-POSS to substitute conventional emulsifier to be polymerized with styrene (St) emulsion obtaining having Pickering effect, and then remove polymer core by the method for solvent etched, thus obtain the hollow structure material that shell is made up of MA-POSS.The adsorbable lyophobic dust of this hollow material, as methylene blue, benzophenone, methyl orange etc., thus can be used for the aspects such as sewage disposal.
The present invention, relative to prior art, has following advantage and beneficial effect:
(1) the present invention is in the preparation process of emulsion, and replace emulsifying agent with MA-POSS part, thus greatly reduce the use of conventional emulsifier, this is of great importance in industrial production; Reduce the use of conventional emulsifier, not only reduce production cost, and greatly reduce the impact of conventional emulsifier on properties of product, make last handling process simpler.
(2) the emulsion microballoon with Pickering effect obtained based on MA-POSS is etched into hollow structure by the present invention first, and the hollow structure material be made up of MA-POSS can effective adsorb both hydrophobic material.
(3) the present invention extends the preparation scope of hollow structure material.Breaking originally only has SiO
2, TiO
2prepare the limitation of hollow structure material Deng inorganic particulate, there is innovative significance.
(4) POSS is successfully prepared into hollow structure material by the present invention, thus also by the premium properties of POSS, as good hot property, mechanical performance etc. are incorporated in polymerizate, thus can improve its performance well.
(5) operating procedure of the present invention is comparatively simple, and experiment condition is gentle, selected raw material, and reagent also all obtains than being easier to, and the productive rate of reaction is high.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope image of the material obtained after the dry also etching of emulsion freeze that embodiment 1 prepares.
Fig. 2 is Fourier's infrared spectrum of the material obtained after the dry also etching of emulsion freeze that embodiment 1 prepares.
Fig. 3 is the ultraviolet phenogram of the solid absorption methylene blue obtained after the dry also etching of emulsion freeze that embodiment 1 prepares.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1: based on the preparation of the hollow structure material of MA-POSS
(1) T is prepared with reference to existing method (disclosed in the Chinese patent application being disclosed as CN103923248A method)
8the content of-MA-POSS accounts for T
8the total content of-MA-POSS and St 10% T
8-MA-POSS plays the emulsion of Pickering effect.
(2) preparation of hollow structure material
The emulsion that above-mentioned steps is obtained carries out drying, cryogenic temperature-55 DEG C, cooling time 24h in freeze drier.Pressed powder is obtained after freeze drying.The volume ratio of configuration acetone and cyclohexane is the mixed solution of 3:7, is soaked in wherein by gained pressed powder.After 12h, filtered, products therefrom natural drying will be filtered, obtained the hollow microsphere based on methacryloxy cage-type silsesquioxane of solid powdery.
(3) get 0.0004g methylene blue to be dissolved in 20ml water, obtain blue liquid, sample preparation 2 parts, the above-mentioned hollow microsphere based on methacryloxy cage-type silsesquioxane of 0.02g will be added in a copy of it, and ultrasonic making it is disperseed.After 2h, observe the dispersion blueness adding hollow sorbing material and obviously shoal, continue to be adsorbed to 12h, then this dispersion color is close to colourless.The dispersion sample getting different time is centrifugal, filters, is carried out ultraviolet spectra test, analyze the change of its methylene blue ultraviolet light absorption intensity.
By the solid dispersal obtained after etching also drying, transmission electron microscope is utilized to observe it.Fig. 1 is TEM figure: as can be seen from Figure, after over etching, the core part of emulsion microballoon is dissolved, and has obvious hollow structure, and hollow microsphere particle diameter is about 70nm.Fig. 2 is Fourier's infrared spectrum of the microballoon after etching, and compares with the spectrogram of PS/MA-POSS emulsion microballoon.In curve a, 1450cm
-1, 1500cm
-1and 1594cm
-1place is the characteristic absorption peak of phenyl ring, shows the existence of PS; 1115cm
-1and 1720cm
-1place is the characteristic absorption peak of Si-O-Si key and carbonyl in MA-POSS.After over etching, 1450cm
-1, 1500cm
-1and 1594cm
-1the characteristic absorption peak of place's phenyl ring obviously weakens, and 1115cm
-1and 1720cm
-1the absworption peak of place's Si-O-Si key and carbonyl is still comparatively strong, and this illustrates that, after the etching of acetone and cyclohexane mixed solvent, most of PS has been dissolved.Still have the existence of part PS, this may be because St and the MA-POSS being positioned at micelle nucleocapsid interface there occurs polymerization, thus is difficult to dissolve.Form primarily of MA-POSS in conjunction with transmission electron microscope picture and infrared spectrum this hollow structure provable, simultaneously containing the PS be polymerized with MA-POSS on a small quantity.Fig. 3 is that obtained hollow structure is to the ultraviolet absorpting spectrum of methylene blue.Find out from this figure, add the hollow material 2h of preparation in methylene blue solution after, the ultraviolet characteristic absorption peak (about 650nm) of methylene blue obviously weakens, after 12h, methylene blue ultraviolet absorption peak almost disappears, and this illustrates that this hollow structure material has good suction-operated to methylene blue.
Embodiment 2: based on the preparation of the hollow structure material of MA-POSS
(1) T is prepared with reference to existing method (disclosed in the Chinese patent application being disclosed as CN103923248A method)
8the content of-MA-POSS accounts for T
8the total content of-MA-POSS and St 10% T
8-MA-POSS plays the emulsion of Pickering effect.
(2) preparation of hollow structure material
The emulsion that above-mentioned steps is obtained carries out drying, cryogenic temperature-55 DEG C, cooling time 24h in freeze drier.Pressed powder is obtained after freeze drying.The volume ratio of configuration acetone and cyclohexane is the mixed solution of 5:5, is soaked in wherein by gained pressed powder.After 18h, filtered, products therefrom natural drying will be filtered, obtained the hollow microsphere based on methacryloxy cage-type silsesquioxane of solid powdery.
(3) get 0.0004g methylene blue to be dissolved in 20ml water, obtain blue liquid, sample preparation 2 parts, the above-mentioned hollow microsphere based on methacryloxy cage-type silsesquioxane of 0.02g will be added in a copy of it, and ultrasonic making it is disperseed.After 2h, observe the dispersion blueness adding hollow sorbing material and obviously shoal, continue to be adsorbed to 12h, then this dispersion color is close to colourless.
Embodiment 3: based on the preparation of the hollow structure material of MA-POSS
(1) T is prepared with reference to existing method (disclosed in the Chinese patent application being disclosed as CN103923248A method)
8the content of-MA-POSS accounts for T
8the total content of-MA-POSS and St 10% T
8-MA-POSS plays the emulsion of Pickering effect.
(2) preparation of hollow structure material
The emulsion that above-mentioned steps is obtained carries out drying, cryogenic temperature-65 DEG C, cooling time 24h in freeze drier.Pressed powder is obtained after freeze drying.The volume ratio of configuration acetone and cyclohexane is the mixed solution of 7:3, is soaked in wherein by gained pressed powder.After 24h, filtered, products therefrom natural drying will be filtered, obtained the hollow microsphere based on methacryloxy cage-type silsesquioxane of solid powdery.
(3) get 0.0004g methylene blue to be dissolved in 20ml water, obtain blue liquid, sample preparation 2 parts, the above-mentioned hollow microsphere based on methacryloxy cage-type silsesquioxane of 0.02g will be added in a copy of it, and ultrasonic making it is disperseed.After 2h, observe the dispersion blueness adding hollow sorbing material and obviously shoal, continue to be adsorbed to 12h, then this dispersion color is close to colourless.
Embodiment 4: based on the preparation of the hollow structure material of MA-POSS
(1) preparation with the emulsion of Pickering effect that MA-POSS is stable
T is prepared with reference to existing method (disclosed in the Chinese patent application being disclosed as CN103923248A method)
10the content of-MA-POSS accounts for T
10the total content of-MA-POSS and St 5% T
10-MA-POSS plays the emulsion of Pickering effect.
(2) preparation of hollow structure material
The emulsion that above-mentioned steps is obtained carries out drying, cryogenic temperature-55 DEG C, cooling time 24h in freeze drier.Pressed powder is obtained after freeze drying.The volume ratio of configuration acetone and cyclohexane is the mixed solution of 3:7, is soaked in wherein by gained pressed powder.After 12h, filtered, products therefrom natural drying will be filtered, obtained the hollow microsphere based on methacryloxy cage-type silsesquioxane of solid powdery.
(3) get 0.0004g methylene blue to be dissolved in 20ml water, obtain blue liquid, sample preparation 2 parts, the above-mentioned hollow microsphere based on methacryloxy cage-type silsesquioxane of 0.02g will be added in a copy of it, and ultrasonic making it is disperseed.After 2h, observe the dispersion blueness adding hollow sorbing material and obviously shoal, continue to be adsorbed to 12h, then this dispersion color is close to colourless.
Embodiment 5: based on the preparation of the hollow structure material of MA-POSS
(1) preparation with the emulsion of Pickering effect that MA-POSS is stable
T is prepared with reference to existing method (disclosed in the Chinese patent application being disclosed as CN103923248A method)
10the content of-MA-POSS accounts for T
10the total content of-MA-POSS and St 5% T
10-MA-POSS plays the emulsion of Pickering effect.
(2) preparation of hollow structure material
The emulsion that above-mentioned steps is obtained carries out drying, cryogenic temperature-55 DEG C, cooling time 24h in freeze drier.Pressed powder is obtained after freeze drying.The volume ratio of configuration acetone and cyclohexane is the mixed solution of 5:5, is soaked in wherein by gained pressed powder.After 18h, filtered, products therefrom natural drying will be filtered, obtained the hollow microsphere based on methacryloxy cage-type silsesquioxane of solid powdery.
(3) get 0.0004g methyl orange to be dissolved in 20ml water, obtain red liquid, sample preparation 2 parts, the above-mentioned hollow microsphere based on methacryloxy cage-type silsesquioxane of 0.02g will be added in a copy of it, and ultrasonic making it is disperseed.After 2h, observe the dispersion redness adding hollow sorbing material and obviously shoal, continue to be adsorbed to 12h, then this dispersion color is close to colourless.
Embodiment 6: based on the preparation of the hollow structure material of MA-POSS
(1) preparation with the emulsion of Pickering effect that MA-POSS is stable
T is prepared with reference to existing method (disclosed in the Chinese patent application being disclosed as CN103923248A method)
10the content of-MA-POSS accounts for T
10the total content of-MA-POSS and St 10% T
10-MA-POSS plays the emulsion of Pickering effect.
(2) preparation of hollow structure material
The emulsion that above-mentioned steps is obtained carries out drying, cryogenic temperature-55 DEG C, cooling time 24h in freeze drier.Pressed powder is obtained after freeze drying.The volume ratio of configuration acetone and cyclohexane is the mixed solution of 7:3, is soaked in wherein by gained pressed powder.After 24h, filtered, products therefrom natural drying will be filtered, obtained the hollow microsphere based on methacryloxy cage-type silsesquioxane of solid powdery.
(3) get 0.0004g methyl orange to be dissolved in 20ml water, obtain red liquid, sample preparation 2 parts, the above-mentioned hollow microsphere based on methacryloxy cage-type silsesquioxane of 0.02g will be added in a copy of it, and ultrasonic making it is disperseed.After 2h, observe the dispersion redness adding hollow sorbing material and obviously shoal, continue to be adsorbed to 12h, then this dispersion color is close to colourless.
Embodiment 7: based on the preparation of the hollow structure material of MA-POSS
(1) preparation with the emulsion of Pickering effect that MA-POSS is stable
T is prepared with reference to existing method (disclosed in the Chinese patent application being disclosed as CN103923248A method)
8the content of-MA-POSS accounts for T
8the total content of-MA-POSS and St 20% T
8-MA-POSS plays the emulsion of Pickering effect.
(2) preparation of hollow structure material
Emulsion obtained for above-mentioned steps is carried out drying in vacuum drying chamber, and temperature is 60 DEG C, drying time 24h.Pressed powder is obtained after drying.The volume ratio of configuration acetone and cyclohexane is the mixed solution of 3:7, is soaked in wherein by gained pressed powder.After 12h, filtered, products therefrom natural drying will be filtered, obtained the hollow microsphere based on methacryloxy cage-type silsesquioxane of solid powdery.
(3) get 0.0004g benzophenone to be dissolved in 20ml water, obtain blue liquid, sample preparation 2 parts, the above-mentioned hollow microsphere based on methacryloxy cage-type silsesquioxane of 0.02g will be added in a copy of it, and ultrasonic making it is disperseed.After 2h, observe the dispersion blueness adding hollow sorbing material and obviously shoal, continue to be adsorbed to 12h, then this dispersion color is close to colourless.
Embodiment 8: based on the preparation of the hollow structure material of MA-POSS
(1) preparation with the emulsion of Pickering effect that MA-POSS is stable
T is prepared with reference to existing method (disclosed in the Chinese patent application being disclosed as CN103923248A method)
8the content of-MA-POSS accounts for T
8the total content of-MA-POSS and St 20% T
8-MA-POSS plays the emulsion of Pickering effect.
(2) preparation of hollow structure material
Emulsion obtained for above-mentioned steps is carried out drying in vacuum drying chamber, and temperature is 60 DEG C, drying time 24h.Pressed powder is obtained after drying.The volume ratio of configuration acetone and cyclohexane is the mixed solution of 5:5, is soaked in wherein by gained pressed powder.After 18h, filtered, products therefrom natural drying will be filtered, obtained the hollow microsphere based on methacryloxy cage-type silsesquioxane of solid powdery.
(3) get 0.0004g benzophenone to be dissolved in 20ml water, obtain blue liquid, sample preparation 2 parts, the above-mentioned hollow microsphere based on methacryloxy cage-type silsesquioxane of 0.02g will be added in a copy of it, and ultrasonic making it is disperseed.After 2h, observe the dispersion blueness adding hollow sorbing material and obviously shoal, continue to be adsorbed to 12h, then this dispersion color is close to colourless.
Embodiment 9: based on the preparation of the hollow structure material of MA-POSS
(1) preparation with the emulsion of Pickering effect that MA-POSS is stable
T is prepared with reference to existing method (disclosed in the Chinese patent application being disclosed as CN103923248A method)
8the content of-MA-POSS accounts for T
8the total content of-MA-POSS and St 20% T
8-MA-POSS plays the emulsion of Pickering effect.
(2) preparation of hollow structure material
Emulsion obtained for above-mentioned steps is carried out drying in vacuum drying chamber, and temperature is 60 DEG C, drying time 24h.Pressed powder is obtained after drying.The volume ratio of configuration acetone and cyclohexane is the mixed solution of 7:3, is soaked in wherein by gained pressed powder.After 24h, filtered, products therefrom natural drying will be filtered, obtained the hollow microsphere based on methacryloxy cage-type silsesquioxane of solid powdery.
(3) get 0.0004g benzophenone to be dissolved in 20ml water, obtain blue liquid, sample preparation 2 parts, the above-mentioned hollow microsphere based on methacryloxy cage-type silsesquioxane of 0.02g will be added in a copy of it, and ultrasonic making it is disperseed.After 2h, observe the dispersion blueness adding hollow sorbing material and obviously shoal, continue to be adsorbed to 12h, then this dispersion color is close to colourless.
Embodiment 10: based on the preparation of the hollow structure material of MA-POSS
(1) preparation with the emulsion of Pickering effect that MA-POSS is stable
T is prepared with reference to existing method (disclosed in the Chinese patent application being disclosed as CN103923248A method)
8the content of-MA-POSS accounts for T
8the total content of-MA-POSS and St 20% T
8-MA-POSS plays the emulsion of Pickering effect.
(2) preparation of hollow structure material
Emulsion obtained for above-mentioned steps is carried out drying in vacuum drying chamber, and temperature is 60 DEG C, drying time 24h.Pressed powder is obtained after drying.Use oxolane as etching agent, gained pressed powder is soaked in wherein.After 12h, pressed powder is all dissolved in wherein, illustrates that oxolane can not as the etching agent constructing hollow microsphere.
Embodiment 11: based on the preparation of the hollow structure material of MA-POSS
(1) preparation with the emulsion of Pickering effect that MA-POSS is stable
T is prepared with reference to existing method (disclosed in the Chinese patent application being disclosed as CN103923248A method)
8the content of-MA-POSS accounts for T
8the total content of-MA-POSS and St 20% T
8-MA-POSS plays the emulsion of Pickering effect.
(2) preparation of hollow structure material
Emulsion obtained for above-mentioned steps is carried out drying in vacuum drying chamber, and temperature is 60 DEG C, drying time 24h.Pressed powder is obtained after drying.Use cyclohexane give is etching agent, is soaked in wherein by gained pressed powder.After 12h, pressed powder becomes thickness, cannot be separated, and illustrates that simple cyclohexane can not as the etching agent constructing hollow microsphere.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1., based on a preparation method for the hollow microsphere of methacryloxy cage-type silsesquioxane, it is characterized in that according to following operating procedure:
(1) emulsion with Pickering effect that methacryloxy cage-type silsesquioxane is stable is prepared, dry, for subsequent use;
(2) adopt the mixed solution of acetone and cyclohexane as etching agent, soak to remove polystyrene core to dried above-mentioned emulsion, filter, obtain the hollow microsphere based on methacryloxy cage-type silsesquioxane.
2. preparation method according to claim 1, is characterized in that: step (1) described drying is boulton process and freeze-drying.
3. preparation method according to claim 2, is characterized in that: the temperature of described boulton process is 60 DEG C, and drying time is 24 hours; Described freeze-drying temperature is-55 ~-57 DEG C, and cooling time is 24 hours.
4. preparation method according to claim 1, is characterized in that: the volume ratio of step (2) described acetone and cyclohexane is 3:7 ~ 7:3.
5. preparation method according to claim 1, is characterized in that: step (2) described immersion is at room temperature carried out, and soak time is 12 ~ 24h.
6. preparation method according to claim 1, it is characterized in that: the preparation of step (1) described emulsion is according to following steps: utilize methacryloxy cage-type silsesquioxane and copolymerization monomer styrene under emulsifying agent effect, in aqueous systems, emulsion reaction obtains pre-emulsion, again by seed emulsion polymerization, under initator effect, polymerisation obtains the emulsion with Pickering effect.
7. preparation method according to claim 6, is characterized in that: the amount of described methacryloxy cage-type silsesquioxane is 10 ~ 30% of copolymerization monomer styrene quality; Described methacryloxy cage-type silsesquioxane is the compound with following structure:
Wherein
8. the hollow microsphere based on methacryloxy cage-type silsesquioxane that method prepares according to any one of claim 1 ~ 7.
9. the application of the hollow microsphere based on methacryloxy cage-type silsesquioxane according to claim 8 in sewage treatment area.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410416125.2A CN104226275B (en) | 2014-08-21 | 2014-08-21 | Hollow microsphere based on methacryloxy cage-type silsesquioxane and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410416125.2A CN104226275B (en) | 2014-08-21 | 2014-08-21 | Hollow microsphere based on methacryloxy cage-type silsesquioxane and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104226275A true CN104226275A (en) | 2014-12-24 |
| CN104226275B CN104226275B (en) | 2016-08-24 |
Family
ID=52215699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410416125.2A Active CN104226275B (en) | 2014-08-21 | 2014-08-21 | Hollow microsphere based on methacryloxy cage-type silsesquioxane and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104226275B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861098A (en) * | 2015-04-28 | 2015-08-26 | 中科院广州化学有限公司 | Star polymer with pH stimulating responsiveness, preparation method thereof and application |
| CN106188573A (en) * | 2016-08-05 | 2016-12-07 | 中科院广州化学有限公司 | PH response emulsion that a kind of star-type polymer is stable and preparation method and application |
| CN106543332A (en) * | 2016-10-13 | 2017-03-29 | 中科院广州化学有限公司 | It is a kind of to be coated with Pickering emulsions of coagent and preparation method thereof |
| CN116063981A (en) * | 2022-12-29 | 2023-05-05 | 中科院广州化学有限公司 | High-temperature-resistant anaerobic adhesive with functional cage-type silsesquioxane structure, and preparation method and application thereof |
| CN116219637A (en) * | 2023-02-08 | 2023-06-06 | 国科广化精细化工孵化器(南雄)有限公司 | Radiation refrigeration film containing polymer microspheres and preparation and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002081205A1 (en) * | 2001-04-04 | 2002-10-17 | Exxonmobil Oil Corporation | Multilayer films including anti-block |
| CN101244377A (en) * | 2008-03-18 | 2008-08-20 | 西北大学 | Polymer absorbing agent and preparation thereof |
| CN103193980A (en) * | 2013-04-03 | 2013-07-10 | 山东大学 | Imidazolyl polysilsesquioxane adsorbent material, and preparation method and application thereof |
| CN103214509A (en) * | 2013-03-25 | 2013-07-24 | 中科院广州化学有限公司 | Cubic eight-methacryloyloxy silsesquioxane crystal and preparation method thereof |
| CN103285793A (en) * | 2013-06-14 | 2013-09-11 | 复旦大学 | Method for preparing hollow polymer microsphere coated with phase change material |
| CN103923248A (en) * | 2014-04-01 | 2014-07-16 | 中科院广州化学有限公司 | Stable methylacryloyl cage type silsesquioxane emulsion with Pickering effect and preparation thereof |
-
2014
- 2014-08-21 CN CN201410416125.2A patent/CN104226275B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002081205A1 (en) * | 2001-04-04 | 2002-10-17 | Exxonmobil Oil Corporation | Multilayer films including anti-block |
| CN101244377A (en) * | 2008-03-18 | 2008-08-20 | 西北大学 | Polymer absorbing agent and preparation thereof |
| CN103214509A (en) * | 2013-03-25 | 2013-07-24 | 中科院广州化学有限公司 | Cubic eight-methacryloyloxy silsesquioxane crystal and preparation method thereof |
| CN103193980A (en) * | 2013-04-03 | 2013-07-10 | 山东大学 | Imidazolyl polysilsesquioxane adsorbent material, and preparation method and application thereof |
| CN103285793A (en) * | 2013-06-14 | 2013-09-11 | 复旦大学 | Method for preparing hollow polymer microsphere coated with phase change material |
| CN103923248A (en) * | 2014-04-01 | 2014-07-16 | 中科院广州化学有限公司 | Stable methylacryloyl cage type silsesquioxane emulsion with Pickering effect and preparation thereof |
Non-Patent Citations (1)
| Title |
|---|
| SHENGLIN YANG，ET AL: "Synthesis of Polystyrene/Polysilsesquioxane Core/Shell Composite Particles via Emulsion Polymerization in the Existence of Poly( γ -Methacryloxypropyl trimethoxysilane) Sol", 《LANGMUIR》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861098A (en) * | 2015-04-28 | 2015-08-26 | 中科院广州化学有限公司 | Star polymer with pH stimulating responsiveness, preparation method thereof and application |
| CN106188573A (en) * | 2016-08-05 | 2016-12-07 | 中科院广州化学有限公司 | PH response emulsion that a kind of star-type polymer is stable and preparation method and application |
| CN106188573B (en) * | 2016-08-05 | 2018-08-07 | 中科院广州化学有限公司 | A kind of pH responses lotion and preparation method and application that star-type polymer is stablized |
| CN106543332A (en) * | 2016-10-13 | 2017-03-29 | 中科院广州化学有限公司 | It is a kind of to be coated with Pickering emulsions of coagent and preparation method thereof |
| CN116063981A (en) * | 2022-12-29 | 2023-05-05 | 中科院广州化学有限公司 | High-temperature-resistant anaerobic adhesive with functional cage-type silsesquioxane structure, and preparation method and application thereof |
| CN116219637A (en) * | 2023-02-08 | 2023-06-06 | 国科广化精细化工孵化器(南雄)有限公司 | Radiation refrigeration film containing polymer microspheres and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104226275B (en) | 2016-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104226275A (en) | Hollow microsphere based on methacrylic acyloxy cage-like silsesquioxane and preparation method and application thereof | |
| Ong et al. | Poly (3-hydroxybutyrate)-functionalised multi-walled carbon nanotubes/chitosan green nanocomposite membranes and their application in pervaporation | |
| Mushi et al. | Strong and tough chitin film from α-chitin nanofibers prepared by high pressure homogenization and chitosan addition | |
| EP2054150B1 (en) | Hydrophobically coated molecular sieve | |
| CN107353886B (en) | CO is prevented to fine and close oil reservoir 2Gas channeling nano composite material and preparation method thereof | |
| CN102674312B (en) | Water soluble fullerene and preparation method thereof | |
| CN103962074B (en) | A kind of hollow sub-micron, its preparation method and application | |
| WO2013016982A1 (en) | Cellulose acetate microsphere preparation method and product prepared thereby | |
| CN1662590A (en) | Carbon nanotube-filled composites | |
| Sun et al. | Preparation and characterization of C60‐filled ethyl cellulose mixed‐matrix membranes for gas separation of propylene/propane | |
| CN103923248A (en) | Stable methylacryloyl cage type silsesquioxane emulsion with Pickering effect and preparation thereof | |
| CN108745321B (en) | For separating the preparation method of the virtual template molecular blotting magnetic microsphere of anthocyanin | |
| Lin et al. | Optically active hollow nanoparticles constructed by chirally helical substituted polyacetylene | |
| WO2013135100A1 (en) | Cellulose based - silicon hybridized microsphere and preparation method thereof | |
| CN107163268B (en) | Hollow bowl-shaped nano silicon dioxide two-dimensional array structure and preparation and application thereof | |
| TW201406848A (en) | Composite and manufacturing method thereof | |
| JP2010254548A (en) | Colloidal silica and method for producing the same | |
| KR100913272B1 (en) | Preparation method of core-shell type nanocomposite particles in supercritical carbon dioxide | |
| CN107999019B (en) | Amphiphilic magnetic nanosphere and preparation method and adsorption application thereof | |
| CN102964540B (en) | Preparation method of solid absorbant for adsorbing flavonoids | |
| US8268175B2 (en) | Method for transferring inorganic oxide nanoparticles from aqueous phase to organic phase | |
| CN113045780B (en) | Polymer material with light-regulated reversible morphology transformation and preparation method and application thereof | |
| CN103073682B (en) | Method for preparing temperature sensitive galactose vinyl ester nano particles by electric spray method | |
| JP2016044091A (en) | Mesoporous silica particle coated with nonporous silica, and method for producing the same | |
| CN111423596B (en) | Trackable auxiliary agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |