CN109957054A - A kind of preparation method of the monodispersity nanoscale polystyrene microsphere of size tunable - Google Patents
A kind of preparation method of the monodispersity nanoscale polystyrene microsphere of size tunable Download PDFInfo
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- CN109957054A CN109957054A CN201910231622.8A CN201910231622A CN109957054A CN 109957054 A CN109957054 A CN 109957054A CN 201910231622 A CN201910231622 A CN 201910231622A CN 109957054 A CN109957054 A CN 109957054A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
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Abstract
The present invention provides a kind of preparation method of the monodispersity nanoscale polystyrene microsphere of size tunable, and the method evenly spreads to aspartic acid in ethanol solution and styrene monomer is uniformly mixed and obtains mixed system A；It is kept stirring state at 60-70 DEG C, azo-initiator is added dropwise with constant speed into mixed system A, insulation reaction after dropwise reaction, dropwise reaction and insulation reaction carry out under conditions of having microwave and ultrasound at the same time；Clean obtained product and separation.The method of the present invention efficiently prepares the monodispersity nanoscale polystyrene microsphere of size tunable by poly-aspartate dispersion microwave supplemental polymeric；Microwave priming reaction greatly improves reaction efficiency, can complete to react in 2.5h, and the conversion ratio of reaction monomers styrene reaches 99.9%；Regulate and control the particle size of nanoscale polystyrene microsphere by regulation poly-aspartate simultaneously；The accurate control of initiator flow greatly improves the homogeneity and monodispersity of polystyrene microsphere.
Description
Technical field
The invention belongs to field of polymer chemical industry, and in particular to a kind of monodispersity nanometer polystyrene of size tunable
The preparation method of microballoon.
Background technique
Nanometer-sized monodisperse polystyrene spheres large specific surface area as possessed by the size of its monodisperse homogeneous grain diameter
With high reactivity and with extremely excellent performances such as excellent absorption property, mechanical performance and stable chemical performances.
Therefore, it is each that optical imagery, water-repellent paint, clinical diagnosis, information engineering microelectric technique, biological detection etc. are widely applied to
Field.
Therefore, it designs and prepares a kind of monodispersity nanoscale polystyrene microsphere of size tunable with highly important
Meaning.
There are a large amount of research and report for the preparation method of the polystyrene microsphere of synthesis nano at present, but still
There is a large amount of problems.As Yang Yanzhao et al. (patent No.: CN 107082837A) reports a kind of partial size and surface charge is controllable
Monodisperse polystyrene microsphere preparation method, i.e., by the reaction system be added solvent, dispersing agent, comonomer,
PH adjusting agent and charge stable agent are uniformly mixed, and are heated to 90-100 DEG C under nitrogen protection, final reaction terminates by multiple
Centrifugation obtains product.But a large amount of pH adjusting agents of the method addition and charge stable agent, high expensive, and it is anti-at 90-100 DEG C
It answers, consumes big energy, waste of energy；Xiao Kaijun et al. (patent No.: CN 107556412A) discloses a kind of micron order sulfonation
Styrene monomer, dispersing agent and initiator are added in dehydrated alcohol by polystyrene microsphere and the preparation method and application thereof,
It is warming up to 65-78 DEG C of reaction 10-24h, solid product is washed, dry, obtains polystyrene microsphere, then that polystyrene is micro-
Ball is added in the concentrated sulfuric acid, 30-80 DEG C of sulfonating reaction 8-24h, and reaction product is washed, dry, obtains micron order sulfonated polyphenyl
Ethylene microballoon.Plum firewood et al. (patent No.: CN 102675501A) has invented a kind of preparation method of polystyrene microsphere, i.e.,
By the way that emulsifier and water are added in three-necked flask, a certain amount of reaction monomers are added, pre-emulsification 0.5-2.5 hours, are heated up
It is added dropwise initiator for reaction 12-48 hours to 65-90 DEG C, and under nitrogen protection, finally by repeatedly being centrifuged repeatedly to obtain polyphenyl
Ethylene microballoon.But the preparation method reported at present is due to complex steps complexity, and expensive raw material price, the reaction time is too long, effect
Rate is low, has for fields such as common application field such as multifunctional coating, medical detection, information engineering microelectric techniques very big
Limitation.
Summary of the invention
A kind of monodisperse of size tunable is provided it is an object of the invention to overcome the shortcomings of the prior art place
The preparation method of property nanoscale polystyrene microsphere.
To achieve the above object, the technical scheme adopted by the invention is as follows: a kind of monodispersity nanoscale of size tunable is poly-
The preparation method of phenylethylene micro ball, the described method comprises the following steps:
(1) aspartic acid (PASP) is evenly spread in ethanol solution, by styrene monomer and is dispersed with aspartic acid
Ethanol solution be uniformly mixed, obtain mixed system A；
(2) it keeps mixed system A to be in stirring at 60-70 DEG C, is added dropwise into mixed system A with constant speed
Azo-initiator continues at 60-70 DEG C of insulation reaction 1-2.5h after dropwise reaction 1-2h, and dropwise reaction and insulation reaction are same
When have microwave and ultrasound under conditions of carry out；
(3) product obtained with ethyl alcohol and ultrapure water alternating cleaning step (2) separates and collects drying after solid product.
The present invention regulates and controls reaction dissolvent medium, greatly improves the anti-of polystyrene by microwave-assisted polymerization reaction
Efficiency is answered, reaction can be completed in 2.5h, the conversion ratio of reaction monomers styrene reaches 99.9%；Select aspartic acid as
Dispersing agent, so that the monodispersity of polystyrene microsphere and homogeneity are more preferable；In conjunction with microsyringe precise control of flew method, by
The mode of sample introduction is added dropwise in drop, and the polystyrene microsphere monodispersity index (PDI) synthesized with this condition is 0.1-0.2, is conducive to
The monodispersity and homogeneity of polystyrene microsphere are controlled, required micron order polystyrene microsphere can be obtained by not needing to separate step by step.
Preferably, it is 1%-5% that aspartic acid, which is distributed to the mass concentration in ethanol solution,.
Preferably, it is 1%, 3% or 5% that aspartic acid, which is distributed to the mass concentration in ethanol solution,.
Inventors discovered through research that can be with high efficiency regulatory as the additive amount of dispersion stabilizer by adjusting poly- aspartic acid
The particle size of nanoscale polystyrene microsphere.
Preferably, the reaction temperature in step (2) is 65 DEG C.
Preferably, the speed that initiator is added dropwise in step (2) is 10ml/h.
Preferably, the speed that initiator is added dropwise in step (2) passes through microsyringe accurate flow control.
Preferably, the time of dropwise reaction is 2h in step (2), and the time of insulation reaction is 2.5h.
Preferably, power ultrasonic in step (2) is 600W.
Preferably, the power of microwave is 800W in step (2).
Preferably, the method for solid product is separated and collected in step (3) as centrifugation, the speed of centrifugation is 6000r/min, step
Suddenly it is room temperature that the temperature dried after solid product is separated and collected in (3).
The present invention also provides a kind of nanoscale polystyrene microsphere that any of the above-described the method is prepared, the nanometers
The partial size of polystyrene microballoon is 350nm-850nm, and the monodispersity index of the nanoscale polystyrene microsphere is 0.1-
0.2。
The beneficial effects of the present invention are: the present invention provides a kind of monodispersity nanometer polystyrenes of size tunable
The preparation method of microballoon efficiently prepares the monodispersity nanoscale of size tunable by poly-aspartate dispersion microwave supplemental polymeric
Polystyrene microsphere；Microwave priming reaction greatly improves reaction efficiency, can complete to react in 2.5h, and reacts single
The conversion ratio of body styrene reaches 99.9%；Regulate and control the grain of nanoscale polystyrene microsphere by regulation poly-aspartate simultaneously
Diameter size；The accurate control of initiator flow greatly improves the homogeneity and monodispersity of polystyrene microsphere.
Detailed description of the invention
Fig. 1 is the polystyrene microsphere phenogram that the embodiment of the present invention is prepared, wherein a: polystyrene microsphere SEM
Figure, b: polystyrene microsphere grain size distribution.
Fig. 2 is the polystyrene microsphere phenogram that the embodiment of the present invention is prepared, wherein a: polystyrene microsphere SEM
Figure, b: polystyrene microsphere grain size distribution.
Fig. 3 is the polystyrene microsphere phenogram that the embodiment of the present invention is prepared, wherein a: polystyrene microsphere SEM
Figure, b: polystyrene microsphere grain size distribution.
Fig. 4 is the polystyrene microsphere phenogram that comparative example of the present invention is prepared.
Fig. 5 is the polystyrene microsphere phenogram that comparative example of the present invention is prepared.
Fig. 6 is the reaction unit schematic diagram that the embodiment of the present invention prepares polystyrene microsphere.
Specific embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention
It is described further.
The reaction unit figure of polystyrene microsphere of the present invention as shown in fig. 6, following embodiment and comparative example polystyrene
The preparation of microballoon carries out in reaction unit schematic diagram as shown in FIG. 6.
Embodiment 1
A kind of preparation method of the monodispersity nanoscale polystyrene microsphere of size tunable as the embodiment of the present invention,
It the described method comprises the following steps:
(1) poly-aspartate is evenly spread in ethanol solution, it is dense that aspartic acid is distributed to the quality in ethanol solution
Degree is 5%, and styrene monomer and the ethanol solution for being dispersed with aspartic acid are placed in continuing magnetic force in three-necked flask reaction unit
Stirring, obtains reaction system A；
(2) reaction system A microwave is warming up to 65 DEG C, azo is added dropwise with the sample introduction speed of 10ml/h using microsyringe
Class initiator continues at 65 DEG C of insulation reaction 2.5h after dropwise reaction 2h, and dropwise reaction and insulation reaction have microwave at the same time
It is carried out under conditions of ultrasound；
(3) product 3 times for being centrifuged repeatedly that cleaning step (2) obtains using dehydrated alcohol and ultrapure water, finally do at room temperature
Dry recycling white powder, wherein centrifugal speed is 6000r/min.
The apparent form scanning electron microscope (SEM) photograph of the polystyrene microsphere prepared in the present embodiment is as shown in Figure 1a；Such as Fig. 1 b institute
Show, for the partial size integrated distribution of nanoscale polystyrene microsphere in 400-500nm, average grain diameter is about 450nm, monodispersity index
It is 0.128.
Embodiment 2
A kind of preparation method of the monodispersity nanoscale polystyrene microsphere of size tunable as the embodiment of the present invention,
It the described method comprises the following steps:
(1) poly-aspartate is evenly spread in ethanol solution, it is dense that aspartic acid is distributed to the quality in ethanol solution
Degree is 3%, and styrene monomer and the ethanol solution for being dispersed with aspartic acid are placed in continuing magnetic force in three-necked flask reaction unit
Stirring, obtains reaction system A；
(2) reaction system A microwave is warming up to 65 DEG C, azo is added dropwise with the sample introduction speed of 10ml/h using microsyringe
Class initiator continues at 65 DEG C of insulation reaction 2.5h after dropwise reaction 2h, and dropwise reaction and insulation reaction have microwave at the same time
It is carried out under conditions of ultrasound；
(3) product 3 times for being centrifuged repeatedly that cleaning step (2) obtains using dehydrated alcohol and ultrapure water, finally do at room temperature
Dry recycling white powder, wherein centrifugal speed is 6000r/min.
The apparent form scanning electron microscope (SEM) photograph of the polystyrene microsphere prepared in the present embodiment is as shown in Figure 2 a；Such as Fig. 2 b institute
Show, for the partial size integrated distribution of nanoscale polystyrene microsphere in 550-650nm, average grain diameter is about 600nm, monodispersity index
It is 0.136.
Embodiment 3
A kind of preparation method of the monodispersity nanoscale polystyrene microsphere of size tunable as the embodiment of the present invention,
It the described method comprises the following steps:
(1) poly-aspartate is evenly spread in ethanol solution, it is dense that aspartic acid is distributed to the quality in ethanol solution
Degree is 1%, and styrene monomer and the ethanol solution for being dispersed with aspartic acid are placed in continuing magnetic force in three-necked flask reaction unit
Stirring, obtains reaction system A；
(2) reaction system A microwave is warming up to 65 DEG C, azo is added dropwise with the sample introduction speed of 10ml/h using microsyringe
Class initiator continues at 65 DEG C of insulation reaction 2.5h after dropwise reaction 2h, and dropwise reaction and insulation reaction have microwave at the same time
It is carried out under conditions of ultrasound；
(3) product 3 times for being centrifuged repeatedly that cleaning step (2) obtains using dehydrated alcohol and ultrapure water, finally do at room temperature
Dry recycling white powder, wherein centrifugal speed is 6000r/min.
The apparent form scanning electron microscope (SEM) photograph of the polystyrene microsphere prepared in the present embodiment is as shown in Figure 3a；Such as Fig. 3 b institute
Show, for the partial size integrated distribution of nanoscale polystyrene microsphere in 650-750nm, average grain diameter is about 700nm, monodispersity index
It is 0.152.
Comparative example 1
A kind of preparation method of the monodispersity nanoscale polystyrene microsphere of size tunable as comparative example of the present invention,
It the described method comprises the following steps:
(1) polyvinylpyrrolidone is evenly spread in ethanol solution, polyvinylpyrrolidone is distributed to ethanol solution
In mass concentration be 5%, by styrene monomer and be dispersed with the ethanol solution of polyvinylpyrrolidone to be placed in three-necked flask anti-
It answers continuing magnetic force in device to stir, obtains reaction system A；
(2) reaction system A microwave is warming up to 65 DEG C, idol is added dropwise to the sample introduction speed of 10ml/h using microsyringe
Nitrogen class initiator continues at 65 DEG C of insulation reaction 2.5h after dropwise reaction 2h, and dropwise reaction and insulation reaction have micro- at the same time
It is carried out under conditions of wave and ultrasound；
(3) product 3 times for being centrifuged repeatedly that cleaning step (2) obtains using dehydrated alcohol and ultrapure water, finally do at room temperature
Dry recycling white powder, wherein centrifugal speed is 6000r/min.
The polystyrene microsphere scanning electron microscope (SEM) photograph that this comparative example is prepared is as shown in figure 4, comparative example 1-3 and comparison
The scanning electron microscope (SEM) photograph of example finds that the homogeneity of the polystyrene microsphere of embodiment 1-3 and dispersibility are substantially better than comparative example 1, this
The homogeneity and dispersibility for the polystyrene microsphere that comparative example is prepared are decreased obviously very much.
Comparative example 2
A kind of preparation method of the monodispersity nanoscale polystyrene microsphere of size tunable as comparative example of the present invention,
It the described method comprises the following steps:
(1) glucoside is evenly spread in ethanol solution, glucoside is distributed to the mass concentration in ethanol solution
It is 5%, styrene monomer is placed in three-necked flask reaction unit with the ethanol solution for being dispersed with polyvinylpyrrolidone and is continued
Magnetic agitation obtains reaction system A；
(2) reaction system A microwave is warming up to 65 DEG C, idol is added dropwise to the sample introduction speed of 10ml/h using microsyringe
Nitrogen class initiator continues at 65 DEG C of insulation reaction 2.5h after dropwise reaction 2h, and dropwise reaction and insulation reaction have micro- at the same time
It is carried out under conditions of wave and ultrasound；
(3) product 3 times for being centrifuged repeatedly that cleaning step (2) obtains using dehydrated alcohol and ultrapure water, finally do at room temperature
Dry recycling white powder, wherein centrifugal speed is 6000r/min.
The polystyrene microsphere scanning electron microscope (SEM) photograph that this comparative example is prepared is as shown in figure 5, comparative example 1-3 and comparison
The scanning electron microscope (SEM) photograph of example finds that the homogeneity of the polystyrene microsphere of embodiment 1-3 and dispersibility are substantially better than comparative example 2, this
The homogeneity and dispersibility for the polystyrene microsphere that comparative example is prepared are decreased obviously very much, illustrate that poly-aspartate is selected to make
It can make the homogeneity of polystyrene microsphere and dispersibility that there is better effect to prepare the dispersing agent of polystyrene.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (10)
1. a kind of preparation method of the monodispersity nanoscale polystyrene microsphere of size tunable, which is characterized in that the method
The following steps are included:
(1) aspartic acid is evenly spread in ethanol solution, by styrene monomer and the ethanol solution for being dispersed with aspartic acid
It is uniformly mixed, obtains mixed system A；
(2) it keeps mixed system A to be in stirring at 60-70 DEG C, azo is added dropwise with constant speed into mixed system A
Class initiator continues at 60-70 DEG C of insulation reaction 1-2.5h after dropwise reaction 1-2h, and dropwise reaction and insulation reaction have at the same time
Have microwave and ultrasound under conditions of carry out；
(3) product obtained with ethyl alcohol and ultrapure water alternating cleaning step (2) separates and collects drying after solid product.
2. the method according to claim 1, wherein aspartic acid is distributed to the mass concentration in ethanol solution is
1%-5%.
3. according to the method described in claim 2, it is characterized in that, aspartic acid is distributed to the mass concentration in ethanol solution is
1%, 3% or 5%.
4. the method according to claim 1, wherein the reaction temperature in step (2) is 65 DEG C.
5. the method according to claim 1, wherein step (2) in be added dropwise initiator speed by it is micro into
Sample device accurate flow control, the middle speed that initiator is added dropwise of step (2) is 10ml/h.
6. the method according to claim 1, wherein the time of dropwise reaction is 2h, insulation reaction in step (2)
Time be 2.5h.
7. the method according to claim 1, wherein power ultrasonic in step (2) is 600W.
8. the method according to claim 1, wherein the power of microwave is 800W in step (2).
9. the method according to claim 1, wherein separated and collected in step (3) solid product method be from
The heart, the speed of centrifugation are 6000r/min, and it is room temperature that the temperature dried after solid product is separated and collected in step (3).
10. a kind of nanoscale polystyrene microsphere being prepared such as any the method for claim 1-9, which is characterized in that
The partial size of the nanoscale polystyrene microsphere is 350nm-850nm, the monodispersity index of the nanoscale polystyrene microsphere
For 0.1-0.2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111941681A (en) * | 2020-09-17 | 2020-11-17 | 凯瑞环保科技股份有限公司 | Device and method for producing polystyrene uniform balls |
| CN115449345A (en) * | 2022-08-29 | 2022-12-09 | 内蒙古科技大学 | Preparation method of mesoporous cerium oxide coated polystyrene nano composite abrasive under microwave condition |
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| WO2003006473A1 (en) * | 2001-07-11 | 2003-01-23 | Lg Chem, Ltd. | Novel multinuclear half metallocene catalyst and preparation of styrene polymer using the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111941681A (en) * | 2020-09-17 | 2020-11-17 | 凯瑞环保科技股份有限公司 | Device and method for producing polystyrene uniform balls |
| CN115449345A (en) * | 2022-08-29 | 2022-12-09 | 内蒙古科技大学 | Preparation method of mesoporous cerium oxide coated polystyrene nano composite abrasive under microwave condition |
| CN115449345B (en) * | 2022-08-29 | 2023-08-22 | 内蒙古科技大学 | Preparation method of mesoporous cerium oxide coated polystyrene nano-composite abrasive under microwave condition |
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Application publication date: 20190702 |