CN104017143A - Silicon dioxide/poly(styrene-methyl methacrylate) nonspherical composite microspheres and preparation method thereof - Google Patents
Silicon dioxide/poly(styrene-methyl methacrylate) nonspherical composite microspheres and preparation method thereof Download PDFInfo
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- CN104017143A CN104017143A CN201410178677.4A CN201410178677A CN104017143A CN 104017143 A CN104017143 A CN 104017143A CN 201410178677 A CN201410178677 A CN 201410178677A CN 104017143 A CN104017143 A CN 104017143A
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Abstract
The invention discloses silicon dioxide/poly(styrene-methyl methacrylate) nonspherical composite microspheres and a preparation method thereof. The preparation method is characterized in that silicon dioxide coated polystyrene microspheres are prepared by adopting a bi-insitu miniemulsion method and utilizing the phase separation effect of increasing polystyrene and ethyl orthosilicate, the in-situ hydrolysis of the ethyl orthosilicate and the in-situ polymerization of styrene, and then a second monomer methyl methacrylate is dropwise added so as to prepare the silicon dioxide/poly(styrene-methyl methacrylate) nonspherical composite microspheres. The preparation method provided by the invention is simple in process, easy to operate, mild in reaction conditions and easy to control; the obtained microspheres have good monodispersity; and the corresponding nonspherical structure is controlled by changing the amount of a modifying agent gamma-methacryloxy propyl trimethoxyl silane.
Description
Technical field
The invention belongs to field of nanocomposite materials, relate in particular to silicon-dioxide/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere and preparation method thereof.
Background technology
Inorganic nano-particle/polymer microballoon has the two-fold advantage of inorganic nano-particle and polymkeric substance concurrently, cause extensive concern and research in academia and industry member, more extensive to the pattern research of complex microsphere at present, pattern has important impact to material function, different patterns can give microballoon different performances, thereby meets people to the high performance requirement of material.And adopt different ingredients and polymerization technique, scholar obtain the special appearances such as " core-shell " structure, " strawberry type " structure, " petal-shaped " structure inorganic/polymer composite microsphere.Wherein the research of the particle to non-spherical morphology is also day by day deep.The polymerization mechanism of miniemulsion is droplet nucleation, and wherein each drop can be used as the reactor of a polyreaction, can greatly improve the clad ratio of inorganic particulate, and this method easy handling, step are simple; Therefore this method is more conducive to prepare Inorganic Nano-Particle/Polymer Composite.Two original position mini-emulsion polymerizations are that inorganic precursors TEOS and monomer are mixed, prepare monomer droplet, in polymerization process, realize the hydrolytic condensation of TEOS and the polyreaction of monomer is synchronously carried out, one step is prepared the hybrid particle that contains silicon-dioxide/polymkeric substance, then drip the second monomer, the squeezing action that is subject to crosslinked seed microballoon, forms multiple projections at microsphere surface, thereby prepares non-spherical complex microsphere.
At present, the application and research of non-spherical complex microsphere has obtained extensive concern, and it can give particle extra performance, as improve optical property, regulate the rheological property of fluid, as the self-assembly unit of biomaterial, for Pickering emulsifying agent etc.; In academic angle and potential application, there is very large prospect; But, in the synthetic method of non-spherical complex microsphere, exist at present the defects such as repeatability controllability poor, shape is low, preparation process is loaded down with trivial details and yield poorly, particularly on preparation shape and uniform monodisperse polymer micro-sphere, need further to be studied, in addition, its application does not also obtain real industrialization, therefore, not only need from now on novel non-sphere complex microsphere of further research and design and preparation method thereof, also will actively expand its application in industrialization.
Summary of the invention
The object of this invention is to provide a kind of silicon-dioxide/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere and preparation method thereof.
The present invention adopts following technical scheme to achieve these goals:
Silicon-dioxide/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere, is characterized in that: its be taking polystyrene as core, silicon-dioxide is shell, the non-spherical complex microsphere that polymethylmethacrylate is protrusion of surface; It is to be made up of the raw material of following weight parts:
Vinylbenzene 14
γ-methacryloxypropyl trimethoxy silane 0.5-0.7
Tetraethoxy 6-7
N-Hexadecane 0.4-0.6
Potassium Persulphate 0.10-0.20
Vinylstyrene 0.1-0.3
Methyl methacrylate 7-9
Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate 0.2-0.3
Water 85-95
The ammoniacal liquor 1.2-1.5 of massfraction 28% left and right.
Described silicon-dioxide/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere, is characterized in that: the described non-spherical complex microsphere of silicon-dioxide/poly-(vinylbenzene-methyl methacrylate) adopts original position mini-emulsion polymerization to prepare.
Described silicon-dioxide/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere, it is characterized in that: described silicon-dioxide/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere particle diameter is between 200-300nm, and the particle diameter of silicon dioxide granule is between 10-20nm.
Described silicon-dioxide/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere, is characterized in that: comprise the following steps:
(1) fully dissolve and mix vinylbenzene by weight, n-Hexadecane, γ-methacryloxypropyl trimethoxy silane, n-Hexadecane, tetraethoxy and Vinylstyrene are as oil phase, get by weight again disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and Potassium Persulphate soluble in water as water, oil phase is slowly added in water, pre-emulsification 0.5-1h, under ice-water bath, utilize the thin emulsification 4-6min of high-speed shearing equipment, and be transferred to immediately in there-necked flask, under whipped state, logical nitrogen 0.5-1h is to get rid of system air, at 70-75 DEG C after water-bath 0.5-1h, drip by weight again ammoniacal liquor, continue reaction,
(2) get by weight methyl methacrylate, after step (1) continues about reaction 3h, by the rate of addition of 8 seconds/left and right, methyl methacrylate is joined in reaction system as the second monomer, continue reaction 5-8h, centrifugal, purification, to obtain final product.
Principle of the present invention is: the present invention utilizes the phase separation principle between polymkeric substance and the single silica acid ethyl ester of growth, tetraethoxy is coated on to polymer surfaces, under the effect of ammoniacal liquor, be hydrolyzed, form silicon dioxide granule, rear dropping the second monomer, the squeezing action that is subject to crosslinked seed microballoon, forms multiple projections at microsphere surface, prepares a kind of non-spherical complex microsphere.
Beneficial effect of the present invention:
(1) adopt two original position miniemulsion legal systems for non-sphere complex microsphere, there is raw material cheap and easy to get, reaction conditions gentleness, technique is simple, is easy to control the features such as operation Yi Hang;
(2) features such as the two standby non-sphere complex microspheres of original position miniemulsion legal system of employing, have average particle size little, and monodispersity is better, and pattern is easy to control;
(3) this pair of non-sphere complex microsphere prepared by original position miniemulsion, corresponding non-sphere structure can be controlled by the amount that changes properties-correcting agent γ-methacryloxypropyl trimethoxy silane,, simple and convenient, easy to implement.
(4) preparation of non-sphere complex microsphere, can be in the self-assembly unit of biomaterial, the aspect application such as Pickering emulsifying agent, engineering colloid matrix material.
Brief description of the drawings
Fig. 1 is the transmission electron microscope of silicon-dioxide/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere
Picture, (a) and (b) are the silicon-dioxide/poly-transmission electron microscope picture of (vinylbenzene-methyl methacrylate) non-spherical complex microsphere under different resolution;
Fig. 2 is the scanning electron microscope picture of silicon-dioxide/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere, and (a) and (b) are the silicon-dioxide/poly-scanning electron microscope (SEM) photograph of (vinylbenzene-methyl methacrylate) non-spherical complex microsphere under different resolution.
embodiment,
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1
Prepare silicon-dioxide/polystyrene microsphere and comprise following raw materials according:
14 parts of vinylbenzene
0.5 part of γ-methacryloxypropyl trimethoxy silane
6 parts of tetraethoxys
0.5 part of n-Hexadecane
0.15 part of Potassium Persulphate
0.2 part of Vinylstyrene
0.2 part of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate
90 parts, water
1.5 parts of ammoniacal liquor (massfraction 28%)
Concrete preparation method is as follows:
Take vinylbenzene, n-Hexadecane, γ-methacryloxypropyl trimethoxy silane, n-Hexadecane, tetraethoxy and Vinylstyrene as oil phase, take disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and Potassium Persulphate soluble in water as water, after being uniformly mixed, oil phase slowly adds in water, room temperature magnetic agitation pre-emulsification 30min, then under ice-water bath, utilize the thin emulsification 5min of high-speed shearing equipment, mixture is transferred in the 250mL four-hole round-bottomed flask that thermometer, agitator and reflux condensing tube are housed to logical N under whipped state
230min, then 70 DEG C of reaction 1h of water-bath, drip NH
3h
2o continues reaction.
Prepare silicon-dioxide/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere and comprise following raw materials according:
8 parts of methyl methacrylates
Concrete preparation method is as follows:
Take methyl methacrylate, magnetic agitation mixes, and after above-mentioned steps reaction 3h, starts to be added drop-wise in reaction system by the rate of addition of 8 seconds/, continues reaction 5-8h, and centrifugal, purification, to obtain final product.
Embodiment 2
Prepare silicon-dioxide/polystyrene microsphere and comprise following raw materials according:
14 parts of vinylbenzene
0.6 part of γ-methacryloxypropyl trimethoxy silane
6 parts of tetraethoxys
0.5 part of n-Hexadecane
0.15 part of Potassium Persulphate
0.2 part of Vinylstyrene
0.2 part of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate
90 parts, water
1.5 parts of ammoniacal liquor (massfraction 28%)
Concrete preparation method is as follows:
(with embodiment 1)
The raw material and the concrete preparation method that prepare silicon-dioxide/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere are as follows
(with embodiment 1)
Embodiment 3
Prepare silicon-dioxide/polystyrene microsphere and comprise following raw materials according:
14 parts of vinylbenzene
0.5 part of γ-methacryloxypropyl trimethoxy silane
7 parts of tetraethoxys
0.5 part of n-Hexadecane
0.15 part of Potassium Persulphate
0.2 part of Vinylstyrene
0.2 part of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate
90 parts, water
1.5 parts of ammoniacal liquor (massfraction 28%)
Concrete preparation method is as follows:
(with embodiment 1)
The raw material and the concrete preparation method that prepare silicon-dioxide/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere are as follows:
(with embodiment 1)
Embodiment 4
Prepare silicon-dioxide/polystyrene microsphere and comprise following raw materials according:
14 parts of vinylbenzene
0.6 part of γ-methacryloxypropyl trimethoxy silane
7 parts of tetraethoxys
0.5 part of n-Hexadecane
0.15 part of Potassium Persulphate
0.2 part of Vinylstyrene
0.2 part of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate
90 parts, water
1.5 parts of ammoniacal liquor (massfraction 28%)
Concrete preparation method is as follows:
(with embodiment 1)
The raw material and the concrete preparation method that prepare silicon-dioxide/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere are as follows:
(with embodiment 1).
Claims (4)
1. silicon-dioxide/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere, is characterized in that: its be taking polystyrene as core, silicon-dioxide is shell, the non-spherical complex microsphere that polymethylmethacrylate is protrusion of surface; It is to be made up of the raw material of following weight parts:
Vinylbenzene 14
γ-methacryloxypropyl trimethoxy silane 0.5-0.7
Tetraethoxy 6-7
N-Hexadecane 0.4-0.6
Potassium Persulphate 0.10-0.20
Vinylstyrene 0.1-0.3
Methyl methacrylate 7-9
Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate 0.2-0.3
Water 85-95
The ammoniacal liquor 1.2-1.5 of massfraction 28% left and right.
2. silicon-dioxide according to claim 1/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere, is characterized in that: the described non-spherical complex microsphere of silicon-dioxide/poly-(vinylbenzene-methyl methacrylate) adopts original position mini-emulsion polymerization to prepare.
3. silicon-dioxide according to claim 1/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere, it is characterized in that: described silicon-dioxide/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere particle diameter is between 200-300nm, and the particle diameter of silicon dioxide granule is between 10-20nm.
4. silicon-dioxide as claimed in claim 1/poly-(vinylbenzene-methyl methacrylate) non-spherical complex microsphere, is characterized in that: comprise the following steps:
(1) fully dissolve and mix vinylbenzene by weight, n-Hexadecane, γ-methacryloxypropyl trimethoxy silane, n-Hexadecane, tetraethoxy and Vinylstyrene are as oil phase, get by weight again disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and Potassium Persulphate soluble in water as water, oil phase is slowly added in water, pre-emulsification 0.5-1h, under ice-water bath, utilize the thin emulsification 4-6min of high-speed shearing equipment, and be transferred to immediately in there-necked flask, under whipped state, logical nitrogen 0.5-1h is to get rid of system air, at 70-75 DEG C after water-bath 0.5-1h, drip by weight again ammoniacal liquor, continue reaction,
(2) get by weight methyl methacrylate, after step (1) continues about reaction 3h, by the rate of addition of 8 seconds/left and right, methyl methacrylate is joined in reaction system as the second monomer, continue reaction 5-8h, centrifugal, purification, to obtain final product.
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| CN201410178677.4A CN104017143A (en) | 2014-04-29 | 2014-04-29 | Silicon dioxide/poly(styrene-methyl methacrylate) nonspherical composite microspheres and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448089A (en) * | 2014-11-28 | 2015-03-25 | 湖北大学 | Preparation method of strawberry-type polystyrene-silicon dioxide nanocomposite microspheres |
| CN104528736A (en) * | 2014-12-15 | 2015-04-22 | 天津工业大学 | Self-assembled preparation of silicon dioxide super material in globular structure |
| CN104892833A (en) * | 2015-05-21 | 2015-09-09 | 安徽大学 | Preparation method of polyacrylic acid hollow microgel |
| CN104892816A (en) * | 2015-05-13 | 2015-09-09 | 衡水新光化工有限责任公司 | In-situ nano hybridization styrene-acrylic emulsion and rust-resisting paint using the emulsion as base material |
| CN104892817A (en) * | 2015-05-28 | 2015-09-09 | 浙江大学 | Preparation method of organosilicon styrene-acrylate fine emulsion |
| CN105382711A (en) * | 2015-10-09 | 2016-03-09 | 芜湖市鸿坤汽车零部件有限公司 | Modified silicon oxide resin grinding wheel and preparing method thereof |
| CN107266715A (en) * | 2016-04-08 | 2017-10-20 | 中国石油天然气股份有限公司 | The method of modifying of Nano carbon white |
| CN107266939A (en) * | 2016-04-08 | 2017-10-20 | 中国石油天然气股份有限公司 | The method of modifying of Nano carbon white |
| CN108517024A (en) * | 2018-04-17 | 2018-09-11 | 陕西科技大学 | Pickering fine emulsion polymerizations prepare polyacrylate/nano-ZnO composite leather coating agent and preparation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816274A (en) * | 2012-07-06 | 2012-12-12 | 安徽大学 | Silica/poly(methyl methacrylate-styrene) double-layered composite microsphere and its preparation method |
-
2014
- 2014-04-29 CN CN201410178677.4A patent/CN104017143A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816274A (en) * | 2012-07-06 | 2012-12-12 | 安徽大学 | Silica/poly(methyl methacrylate-styrene) double-layered composite microsphere and its preparation method |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448089A (en) * | 2014-11-28 | 2015-03-25 | 湖北大学 | Preparation method of strawberry-type polystyrene-silicon dioxide nanocomposite microspheres |
| CN104528736A (en) * | 2014-12-15 | 2015-04-22 | 天津工业大学 | Self-assembled preparation of silicon dioxide super material in globular structure |
| CN104892816A (en) * | 2015-05-13 | 2015-09-09 | 衡水新光化工有限责任公司 | In-situ nano hybridization styrene-acrylic emulsion and rust-resisting paint using the emulsion as base material |
| CN104892833A (en) * | 2015-05-21 | 2015-09-09 | 安徽大学 | Preparation method of polyacrylic acid hollow microgel |
| CN104892817A (en) * | 2015-05-28 | 2015-09-09 | 浙江大学 | Preparation method of organosilicon styrene-acrylate fine emulsion |
| CN105382711A (en) * | 2015-10-09 | 2016-03-09 | 芜湖市鸿坤汽车零部件有限公司 | Modified silicon oxide resin grinding wheel and preparing method thereof |
| CN107266715A (en) * | 2016-04-08 | 2017-10-20 | 中国石油天然气股份有限公司 | The method of modifying of Nano carbon white |
| CN107266939A (en) * | 2016-04-08 | 2017-10-20 | 中国石油天然气股份有限公司 | The method of modifying of Nano carbon white |
| CN107266715B (en) * | 2016-04-08 | 2019-06-07 | 中国石油天然气股份有限公司 | The method of modifying of Nano carbon white |
| CN108517024A (en) * | 2018-04-17 | 2018-09-11 | 陕西科技大学 | Pickering fine emulsion polymerizations prepare polyacrylate/nano-ZnO composite leather coating agent and preparation method |
| CN108517024B (en) * | 2018-04-17 | 2020-12-11 | 陕西科技大学 | Polyacrylate/nano ZnO composite leather finishing agent prepared by Pickering miniemulsion polymerization method and preparation method thereof |
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