CN103333280B - A kind of method based on hydrothermal treatment consists regulation and control polystyrene microsphere monodispersity - Google Patents
A kind of method based on hydrothermal treatment consists regulation and control polystyrene microsphere monodispersity Download PDFInfo
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- CN103333280B CN103333280B CN201310240501.2A CN201310240501A CN103333280B CN 103333280 B CN103333280 B CN 103333280B CN 201310240501 A CN201310240501 A CN 201310240501A CN 103333280 B CN103333280 B CN 103333280B
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Abstract
The present invention relates to a kind of regulate and control the method for polystyrene microsphere monodispersity, be specifically related to a kind of method based on hydrothermal treatment consists, the polystyrene micron ball of monodispersity difference being converted into the good Properties of Polystyrene Nano Particles of single dispersing.Monodisperse polystyrene microsphere Application Areas is extensive, but cost is expensive, operation is simple and feasible for the method, the polystyrene microsphere of monodispersity difference is turned waste into wealth, the good Properties of Polystyrene Nano Particles of the monodispersity of different size can be obtained by regulating stabilizer consumption, the preparation cost of remarkable reduction monodisperse polystyrene microsphere, energy-conserving and environment-protective, are beneficial to the recycle of resource.
Description
Technical field
The present invention relates to a kind of regulate and control the method for polystyrene microsphere monodispersity, be specifically related to a kind of method based on hydrothermal treatment consists, the polystyrene micron ball of monodispersity difference being converted into the good Properties of Polystyrene Nano Particles of single dispersing, belong to field of polymer microsphere materials.
Background technology
Polymer microsphere refers to that size is between nano level to micron order, and shape is spherical or the macromolecular material of other solid or polymer composite, and its pattern can be diversified, comprises solid, hollow, porous, dumbbell shape, onion type etc.According to the size distribution of polymer microsphere, polymer microsphere can be divided into single dispersing, narrow dispersion and polydispersion microballoon again.Monodisperse polymer micro-sphere is the novel macromolecular material of a class, because it has highly consistent size and special physical and chemical performance, has a wide range of applications in optics, magnetics, biomedicine, fabrication of new materials etc.There are two large technological difficulties in monodisperse polymer micro-sphere: the control of (1) polyalcohol microspherulite diameter size in preparation process; (2) control (dispersion coefficient≤0.05) of polyalcohol microspherulite diameter distribution.Monodispersed polymer microsphere industrially pole has application potential, but involves great expense, and therefore seems more and more important to the control of polyalcohol microspherulite diameter distribution.
Monodisperse polystyrene (PS) microballoon because of there is excellent hydrophobicity, not biodegradable and size of particles controllability is good, surface reaction activity is high, gelation fortunately many science and technology field have a wide range of applications.At present, existing monodisperse polystyrene microsphere technology of preparing is all limited in by telo merization condition if stablizer, dispersion agent and dispersion medium polarity etc. are because of usually regulation and control synthesis, monodisperse polystyrene microsphere can only be obtained under some specific stoichiometric ratio, can not get the polymer microballoon of size monodisperse in most cases.Therefore, it is possible to propose a kind of simple possible, low cost and the regulate and control method of eco-friendly polystyrene microsphere monodispersity seems particularly urgent.
Hydrothermal method refers to that, in the pressurized vessel of sealing, water is solvent, the chemical reaction carried out under the condition of High Temperature High Pressure.Because its high temperature, high voltage nature are widely used in the synthesis of inorganic nanocrystal, seldom relate to the polymeric material field of poor heat stability.Just because of this, the combination of polymer microballoon and hydrothermal method just has more research potential.The change that polystyrene microsphere is applied to hydrothermal system generation Microsphere Size and monodispersity has relevant report, (Zhang Y, Chu Y, the Dong L.One-step synthesis and properties of urchin-like PS/ α-Fe such as Zhang
2o
3composite hollow microspheres [J] .Nanotechnology, 2007,18 (43): 435608) with the sulfonated polystyrene microballoon PS/ α-Fe that has been templated synthesis
2o
3hybrid hollow microballoon, polystyrene microsphere is melt into PS film under hydrothermal conditions because of poor heat stability.(the Yang Y such as Yang, Chu Y, Zhang Y, et al.Polystyrene-ZnO core-shell microspheres and hollow ZnO structures synthesized with the sulfonated polystyrene templates [J] .Journal of Solid State Chemistry, 2006, 179 (2): 470-475) prepare under hydrothermal conditions in PS/ZnO complex microsphere process and find the sulfonic monodisperse polystyrene microsphere of surperficial unmodified monodispersity variation under hydrothermal conditions, be melt into large size, the polystyrene microsphere that particle diameter differs.Polystyrene micron ball poor for monodispersity is carried out hydrothermal treatment consists and obtains the good Properties of Polystyrene Nano Particles of monodispersity by the present invention innovatively, in the existing regulate and control method about polystyrene microsphere monodispersity, the method based on hydrothermal treatment consists regulation and control polystyrene microsphere monodispersity has not yet to see report.
Summary of the invention
The present invention aim to provide a kind of regulate and control the method for polystyrene microsphere monodispersity, be specifically related to a kind of method based on hydrothermal treatment consists, the polystyrene micron ball of monodispersity difference being converted into the good Properties of Polystyrene Nano Particles of single dispersing.Operation is simple and feasible for the method, greatly can reduce the preparation cost of monodisperse polystyrene microsphere and be beneficial to the recycling of resource.
Object of the present invention is achieved through the following technical solutions:
(1) preparation of polystyrene micron ball
In the three-necked bottle that reflux condensing tube and magnetic stirring apparatus are housed, add a certain amount of stablizer and 39mL solvent, pass into N
2, be warming up to 81 DEG C under stirring and stablizer dissolved, disposablely add the styrene monomer 8.8mL being dissolved with initiator, N
2stirred under argon isothermal reaction 9h obtains polystyrene micron ball emulsion.
The optional Vltra tears of stablizer of the present invention (HPC), polyvinylpyrrolidone (PVP, K30), polyoxyethylene glycol (PEG, molecular weight is greater than 10000), polyacrylic acid (PAA, molecular weight 1000 ~ 5000) any one.
The addition of stablizer of the present invention is amount of monomer 6.0wt% ~ 13.0wt%.
The optional benzoyl peroxide of initiator of the present invention, Diisopropyl azodicarboxylate any one.
Initiator addition of the present invention is amount of monomer 0.8wt% ~ 1.5wt%.
The optional ethanol/water volume ratio of solvent of the present invention is 0.4 ~ 1.0.
(2) polystyrene micron ball hydrothermal treatment consists
Get the aqueous solution that 2mL polystyrene micron ball emulsion prepared by step (1) and 10mL are dissolved with a certain amount of stablizer, transferring to 15mL after ultrasonic 10min contains in the stainless steel cauldron of polytetrafluoroethylliner liner, obtains hydrothermal treatment consists product under certain temperature after hydrothermal treatment consists for some time.
Stablizer of the present invention be polyvinyl alcohol (PVA1788), technical gelatine, Vltra tears, Sodium dodecylbenzene sulfonate, cetyl benzenesulfonic acid sodium, sodium lauryl sulphate, Sodium palmityl sulfate, Trimethyllaurylammonium bromide, cetyl trimethylammonium bromide any one or any two kinds composite.
The addition of stablizer agent of the present invention is the 1.0wt% ~ 5.0wt% of polystyrene micron ball emulsion solid content.
Hydrothermal treatment consists temperature of the present invention is 100 DEG C ~ 140 DEG C.
Hydrothermal conditions of the present invention is 12h ~ 24h.
The innovation that the present invention is based on the regulation and control of hydrothermal treatment consists p-poly-phenyl ethene Microsphere Size is:
(1) control technique of existing polystyrene microsphere monodispersity is mainly by selecting different polymerization processs and regulating stabilizer consumption, initiator amount, dispersion medium polarity etc. prepares the polystyrene microsphere of different size, need in specified chemical metering than obtaining monodisperse polystyrene microsphere, and hydrothermal treatment process of the present invention is equivalent to a polystyrene microsphere " source mill ", by the polystyrene micron ball of monodispersity difference, be processed into the Properties of Polystyrene Nano Particles of size uniformity, there is important practical application be in the industrial production worth, greatly can reduce the preparation cost of monodisperse polystyrene microsphere.
(2) polystyrene microsphere that monodispersity is good is all widely used in every subjects field and cost is more expensive, and polystyrene micron ball poor for monodispersity is converted into the good Properties of Polystyrene Nano Particles of monodispersity by the present invention, turn waste into wealth, be beneficial to the recycle of resource.
(3) by the consumption of stablizer in regulating step 2, the polystyrene micron ball of single dispersing difference can be converted into the good Properties of Polystyrene Nano Particles of different size monodispersity.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the polystyrene micron ball of monodispersity difference prepared by embodiment 1
Fig. 2 is that embodiment 1 polystyrene micron ball is through hydrothermal treatment consists after product scanning electron microscope (SEM) photograph
Fig. 3 is that embodiment 1 polystyrene micron ball is through hydrothermal treatment consists after product grain size distribution
Embodiment
Below by embodiment, the present invention is further illustrated:
1. the preparation of polystyrene micron ball
In the three-necked bottle that reflux condensing tube and magnetic stirring apparatus are housed, add a certain amount of stablizer and 39mL dehydrated alcohol, pass into N
2, be warming up to 81 DEG C under stirring and stablizer dissolved, disposablely add the vinylbenzene 8.8mL being dissolved with 0.08g BPO, N
2stirred under argon isothermal reaction 9h obtains white emulsion.
The polystyrene micron ball of different size monodispersity difference can be prepared by the kind of stablizer in regulating step (1) and consumption.
* stabilizing agent dosage is the mass percent of amount of monomer
2. the hydrothermal treatment consists of polystyrene micron ball
Get the aqueous solution that 2mL polystyrene micron ball emulsion prepared by step (1) and 10mL are dissolved with a certain amount of stablizer, transferring to 15mL after ultrasonic 10min contains in the stainless steel cauldron of polytetrafluoroethylliner liner, obtains hydrothermal treatment consists product after 100 DEG C of isothermal reaction 12h.
The polystyrene micron ball of different size monodispersity difference in embodiment can be converted into the good Properties of Polystyrene Nano Particles of monodispersity by changing stabilizer type and consumption in step (2):
Here still embodiment 1 ~ 5, embodiment divides two steps, and the stabilizer type of two forms is step one and step 2 with consumption respectively.
* stabilizing agent dosage is the mass percent of polystyrene micron ball emulsion solid content.
Claims (9)
1. regulate and control a method for polystyrene microsphere monodispersity, its step is as follows:
(1) preparation of polystyrene micron ball
In the three-necked bottle that reflux condensing tube and magnetic stirring apparatus are housed, add a certain amount of first stablizer and 39 mL solvents, pass into N
2, be warming up to 81 DEG C under stirring and stablizer dissolved, disposablely add styrene monomer 8.8 mL being dissolved with initiator, N
2stirred under argon isothermal reaction 9 h obtains polystyrene micron ball emulsion;
(2) polystyrene micron ball hydrothermal treatment consists
Get the aqueous solution that 2 mL polystyrene micron ball emulsions prepared by step (1) and 10 mL are dissolved with a certain amount of second stablizer, transferring to 15 mL after ultrasonic 10 min contains in the stainless steel cauldron of polytetrafluoroethylliner liner, obtains hydrothermal treatment consists product under certain temperature after hydrothermal treatment consists for some time;
Described second stablizer be PVAC polyvinylalcohol 1788, technical gelatine, Vltra tears, Sodium dodecylbenzene sulfonate, cetyl benzenesulfonic acid sodium, sodium lauryl sulphate, Sodium palmityl sulfate, Trimethyllaurylammonium bromide, cetyl trimethylammonium bromide any one or any two kinds composite.
2. according to claim 1 a kind of regulate and control the method for polystyrene microsphere monodispersity, it is characterized in that described first stablizer is Vltra tears HPC, K value is the polyvinylpyrrolidone PVP of 30, the polyoxyethylene glycol PEG that molecular weight is greater than 10000, molecular weight is at any one of 1000 ~ 5000 polyacrylic acid PAA.
3. according to claim 1 and 2 a kind of regulate and control the method for polystyrene microsphere monodispersity, it is characterized in that the addition of described first stablizer is 6.0 wt% ~ 13.0 wt% of amount of monomer.
4. according to claim 1 a kind of regulate and control the method for polystyrene microsphere monodispersity, it is characterized in that described initiator be benzoyl peroxide, Diisopropyl azodicarboxylate any one.
5. according to claim 1 a kind of regulate and control the method for polystyrene microsphere monodispersity, it is characterized in that described initiator addition is amount of monomer 0.8 wt% ~ 1.5 wt%.
6. according to claim 1 a kind of regulate and control the method for polystyrene microsphere monodispersity, it is characterized in that described solvent is is the aqueous ethanolic solution of 0.4 ~ 1.0 with water volume ratio.
7. according to claim 1 a kind of regulate and control the method for polystyrene microsphere monodispersity, it is characterized in that the addition of described second stablizer is the 1.0wt% ~ 5.0wt% of polystyrene micron ball emulsion solid content.
8. according to claim 1 a kind of regulate and control the method for polystyrene microsphere monodispersity, it is characterized in that described step (2) hydrothermal treatment consists temperature is 100 DEG C ~ 140 DEG C.
9. according to claim 8 a kind of regulate and control the method for polystyrene microsphere monodispersity, it is characterized in that described step (2) hydrothermal conditions is 12h ~ 24h.
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| CN104558316A (en) * | 2014-12-23 | 2015-04-29 | 安徽助成信息科技有限公司 | Method for synthesizing polystyrene microspheres based on emulsion method |
| CN105061649A (en) * | 2015-08-07 | 2015-11-18 | 武汉理工大学 | Synthetic method of polystyrene emulsion with extra-high solid content |
| CN107161989A (en) * | 2016-03-08 | 2017-09-15 | 云南民族大学 | A kind of preparation method of cellular three-dimensional grapheme |
| CN107456929B (en) * | 2017-07-24 | 2020-06-02 | 大连理工大学 | Preparation method and application of monodisperse polysaccharide derivative microspheres |
| CN109553785A (en) * | 2018-12-05 | 2019-04-02 | 哈尔滨工业大学（深圳） | A kind of microfluidic control for micron size polystyrene spheres method |
| CN114456326A (en) * | 2022-02-17 | 2022-05-10 | 武汉纺织大学 | Carboxylated polystyrene nano-microsphere and preparation method and application thereof |
| CN117361970A (en) * | 2023-09-12 | 2024-01-09 | 苏州云孚德新型环保建材有限公司 | Environment-friendly anti-cracking thermal insulation mortar and preparation method thereof |
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