CN102659966A - Polymer microsphere, preparation method and application thereof - Google Patents
Polymer microsphere, preparation method and application thereof Download PDFInfo
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- CN102659966A CN102659966A CN2012101082813A CN201210108281A CN102659966A CN 102659966 A CN102659966 A CN 102659966A CN 2012101082813 A CN2012101082813 A CN 2012101082813A CN 201210108281 A CN201210108281 A CN 201210108281A CN 102659966 A CN102659966 A CN 102659966A
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Abstract
The invention discloses a surface modified polystyrene polymer microsphere, a preparation method and an application thereof. Polystyrene is used as a base sphere and the surface contains a brominated phenyl ring structure which generates pi-pi reaction with fullerene. Hydrogen atoms on the phenyl ring contained by the base sphere are substituted by bromine atoms to obtain the structure. The preparation method comprises the following steps of: using monodispersed polystyrene microsphere with its particle size being 10-40 microns as the base sphere, mixing with a catalyst, adding an aliphatic halogenated hydrocarbon solvent, slowly adding a brominating agent drop by drop with stirring to carry out a substitution reaction, taking out the microsphere, washing, and drying to obtain a polymer microsphere which is used as a liquid chromatographic stationary phase for fullerene separation with toluene or o-xylene as a mobile phase. According to the surface modified polystyrene polymer microsphere, its preparation method only requires one step, has a simple technology, is easy to repeat, is suitable for large-scale production of fullerene and has characteristics of high separation efficiency and good effects.
Description
Technical field
The present invention relates to a kind of PS polymer microsphere, preparation method and application thereof of surface-treated.
Technical background
Soccerballene (Fullerene) is the general name of ball-type, spheroid shape, column type or the tracheary element of the hollow be made up of carbon fully, is the third homoatomic shape allosome [1] of carbon behind diamond and graphite.Before the discovery of soccerballene, the allotropic substance of carbon have only graphite, diamond, decolorizing carbon (like coal ash and charcoal), the number of the allotropic substance of carbon has greatly been expanded in its discovery.Its particular structural gives fullerene-based material the performance excellent at aspects such as superconduction, magnetic, optics, catalysis.As a kind of typical carbon nano-functional material, soccerballene will play an important role market outlook wide [2] in fields such as industry, national defence, the energy, scientific research, biomedicines.This product is put into national new material industry 12 planning forward position novel materials-field of nanometer material technology staple product catalogue [No. 368 product].The large-scale production soccerballene is a technology barriers always, and obtaining highly purified soccerballene product also is one of very important bottleneck.
The preparation of soccerballene is raw material with graphite usually, and product is C
60And C
70Etc. the mixture of multiple soccerballene, because molecular structure is closely similar each other, physicochemical property are very close, separate to have bigger difficulty.Chromatography is one of effective means of present mixture separation, and it has advantages such as good separating effect, velocity of separation be fast, in the soccerballene separation and purification, demonstrates exclusive advantage.Particularly the chromatographic process based on charge transfer mechanism shows higher separation selectivity in the soccerballene separation and purification.Soccerballene contains abundant two keys, and the stationary phase that can be used as electron donor(ED) or electron acceptor(EA) and contain aromatic ring produces π-π and interacts, thereby reaches selective separation.At present most of in the world research and produce the product B uckprep separator column that the soccerballene person uses Japanese COSMOSIL company to produce, the filler that this post uses contains the microballoon of pyrenyl functional group just, this stationary phase can with C
60And C
70Produce π-π interaction etc. multiple soccerballene, can satisfy soccerballene and prepare isolating needs.Simultaneously, the said firm has also produced the soccerballene separating filler that contains pentabromobenzene ethyl functional group, and separating power is 3 times of product B uckprep.But the preparation process of these silica matrix stationary phase is complicated and cost an arm and a leg.This filler belongs to silica matrix simultaneously, and functional group stability is limited easily, and preparation and use can not be used alkaline condition.Particle diameter is merely 5 μ m, thereby the post pressure is bigger, has limited the size scale of preparation separator column, thereby has influenced isolating output, increases use cost.Therefore, need the separating filler of a kind of with low cost and suitable mass preparation of exploitation badly.
Chinese invention patent (CN1108271) discloses a kind of method of manufacture that is used for the isolating performance liquid chromatography stationary phase of soccerballene; Macroporous polystyrene-divinyl phenyl the ball that adopts is to be that raw material, divinylbenzene are linking agent with vinylbenzene; Through suspension polymerization preparation in the presence of pore-creating agent, be reflected in the dispersion system and accomplish.Then basic ball is carried out chemically modified, will with C
60, C
70The 2-that Intermolecular Forces is stronger (3, the 4-xylyl) ethyl is received on the basic ball as separation function group.This stationary phase can use 0-YLENE to be the moving phase separation of C
60, C
70And higher fullerene.Chinese invention patent (CN1114656) discloses a kind of isolating performance liquid chromatography stationary phase of soccerballene 2-(3 that is used for; The 5-xylyl) preparation method of the modified macroporous polystyrene-divinylbenzene stationary phase of ethyl; Adopt two step Friedel-Crafts reactions, at anhydrous AlCl
3There are down macroporous polystyrene-divinyl phenyl ball and 1, the reaction of 2-ethylene dichloride, general-CH
2-CH
2The Cl group is connected on the basic ball, with the reaction of m-YLENE, processes the stationary phase that has 2-(3, the 5-xylyl) ethyl group again.This stationary phase can be a moving phase with 0-YLENE, high efficiency separation C
60And C
70But; The micro-sphere crosslinked degree of this method preparation is lower, and hardness is less, easy swelling in toluene and o-Xylol; Thereby post is pressed higher; Thereby limited its flow velocity in chromatographic applications, this stationary phase of 8-15 μ m allows the flow velocity of moving phase to be merely 0.15-0.25 mL/min, and the preparation sample flash liberation time is more than 200 min.Existing drawbacks limit its large-scale application.Document " 2; 4; 6-trinitrophenol modification zirconium Magnesium coumpoud oxide stationary phase separates the chromatographic property research of soccerballene " ([J]. chromatogram, 2005,23 (4): disclose a kind of usefulness 2 384-388.); 4,6-trinitrophenol modification zirconium Magnesium coumpoud oxide separates the method for soccerballene as stationary phase.The moving phase that this stationary phase uses is the mixture of toluene and hexanaphthene, and when the toluene ratio surpassed 50%, this stationary phase is separation of C well
60And C
70And this stationary phase is contained on the stainless steel column of 150 * 4.6 mm C
60And C
70RT be merely 2～4 min, explain that this stationary phase is to C
60And C
70Save power a little less than, also unsuitable mass preparation is separated soccerballene.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, provide a kind of preparation process simple, be easy to repetition, the suitable amplification is used for the soccerballene good separating effect, polymer microsphere that efficient is high and preparation method thereof.
The technical scheme that realizes the object of the invention provides a kind of polymer microsphere, and it is basic ball with PS, and the interactional bromobenzene ring structure with soccerballene generation π-π is contained on basic ball surface; Described bromobenzene ring structure is replaced by bromine atoms by the Wasserstoffatoms on the contained phenyl ring of basic ball and obtains.
A kind of preparation method of described polymer microsphere comprises the steps:
(1) be that 10～40 μ m, monodispersed polystyrene microsphere are basic ball with particle diameter, after catalyst mix, add the aliphatic halogenated hydrocarbon kind solvent, agitation condition slowly drips bromizating agent down; By weight, the ratio of basic ball and solvent is 1:10～15, the ratio of basic ball and bromizating agent is 1:4.7～7.8; Described catalyzer is reduction Fe powder, or reduction Al and AlCl
3Mixture, wherein, Al and AlCl
3Ratio be 1:1～2; The ratio of base ball and catalyst reduction Fe powder is 1:0.05～0.10, basic ball and catalyst A l and AlCl
3The ratio of mixture be 1:0.06～0.11;
(2) slowly be warming up to 35～50 ℃ and carry out substitution reaction; After reaction finishes, aaerosol solution is reduced to room temperature, add basic soln and carry out neutralization reaction, take out microballoon again,, obtain a kind of polymer microsphere through washing, drying.
Described aliphatic halogenated hydrocarbon kind solvent is a kind of in methylene dichloride, chloroform, tetracol phenixin, the ethylene dichloride or their arbitrary combination.
Described bromizating agent is a kind of or combination in bromine, the bromine chloride.
A kind of application of described polymer microsphere, being used for moving phase is the isolating liquid chromatography stationary phase of soccerballene of toluene or o-Xylol.
Compared with prior art, beneficial effect of the present invention is:
1, the present invention is basic ball with PS, utilizes bromizating agent in hydrochloric ether, to react and generates and can produce the interactional bromobenzene ring structure of π-π title product, good separating effect with soccerballene;
2, step of preparation process only needs can accomplish once going on foot, and is simple and convenient, is easy to control and repeats suitable for industrial;
3, polymer microsphere degree of crosslinking provided by the invention is higher, and particle diameter is big, and hardness is higher; When being applied to the isolating liquid chromatography stationary phase of soccerballene, swelling is low in toluene and o-Xylol, and post is pressed less; Thereby can use higher flow velocity, and improve separation efficiency, help suitability for industrialized production.
Description of drawings
Fig. 1 is the reaction principle synoptic diagram that the embodiment of the invention prepares polymer microsphere.
Fig. 2 is the SEM figure of the polymer microsphere of embodiment of the invention preparation.
Fig. 3 is the polymer microsphere (UniPS 30-300-Br) of embodiment of the invention preparation and the ir spectra comparison diagram of polystyrene-based ball (UniPS 30-300).
Fig. 4 is the design sketch that the polymer microsphere of embodiment of the invention preparation is used to separate soccerballene as stationary phase.
Embodiment
Prepare polystyrene microsphere by the disclosed technical scheme of Chinese invention patent CN101186661, note is made UniPS 30-300.Polystyrene microsphere (the UniPS 30-300 microballoon of prior weighing 40.00 g in the there-necked flask of exsiccant 500 mL; Diameter is about 30 μ m) as basic ball; And 2.00 g iron powders, then, this there-necked flask is pressed dress whisking appliance, spiral condenser and constant pressure funnel successively; The spiral condenser port inserts device for absorbing tail gas, and absorption liquid is a sodium sulfite solution.Elder generation adds the ethylene dichloride solvent of 300 mL in there-necked flask, and microballoon is stirred, and slowly drips bromine 50 mL again in above-mentioned aaerosol solution, and about 30 min dropwise, and there-necked flask is immersed in the ice bath too violent to prevent reaction.Will note airtightly in the there-necked flask reaction process, the sealing-ring of contact reacts solution and steam and pipeline should be corrosion-resistant.Dropwise Deng bromine, slowly be warming up to 50 ℃ to guarantee reacting balance, reaction is spent the night; Referring to accompanying drawing 1, it is the reaction principle synoptic diagram that present embodiment prepares polymer microsphere.After reaction finishes, will react aaerosol solution earlier and reduce to room temperature, slowly add unnecessary bromine and hydrogen bromide in the sodium sulfite solution neutralization reaction suspension-s then.This suspension-s is filtered with sand core funnel; And use acetone, ethanol, water, sodium sulfite solution, water, washing with alcohol microballoon successively; Obtain exsiccant polymer microsphere (note is made UniPS 30-300-Br) after the vacuum-drying, be about 83.29 g, bromine content is 51.98%.
Referring to accompanying drawing 2, it is the SEM figure by the polymer microsphere of embodiment of the invention preparation; Visible by figure, the microspherulite diameter homogeneous belongs to mono-dispersion microballoon.
Referring to accompanying drawing 3, it is the infrared spectrogram by polymer microsphere (UniPS 30-300-Br) with the polystyrene-based ball (UniPS 30-300) of embodiment of the invention preparation; Visible by figure, the microballoon after the modification obviously weakens at the Ar-H at 3050～3100 places stretching vibration absorption peak, proves that bromine modified on the phenyl ring; And 2930～2850 places-CH
2-absorbing and obviously do not weaken, the Wasserstoffatoms at this place is not substituted.
Get the product microballoon 2g of present embodiment preparation, in the stainless steel chromatogram post of the 250*4.6 mm that under 1000 psi pressure, packs into slurry method.Then this post is contained in according on the sharp extra-high-speed effect liquid phase chromatogram appearance, the toluene with 100% is as moving phase, and flow velocity is 1mL/min, and detecting wavelength is 310 nm, and injecting 25 μ L concentration is the soccerballene bullion of 2.5 mg/ml.Referring to accompanying drawing 4, it is that the polymer microsphere of present embodiment preparation is used to separate the design sketch of soccerballene as stationary phase, and is visible by figure, C
60With C
70Basically reach baseline separation.
The diameter of micro ball that present embodiment provides is about 30 μ m, is used as the stationary phase of liquid chromatography, because the particle of this stationary phase is bigger; With respect to the stationary phase of the separation soccerballene of prior art, flow velocity can increase substantially, and no matter is separation efficiency; Or sample separation effect; All demonstrated more satisfactory separating effect, and can reduce the use and the maintenance cost of required instrument, be suitable for mass preparation and separate soccerballene.
Embodiment 2
It is identical with enforcement 1 that reaction unit and tail gas absorb.Weighing 10.00 g press PS UniPS 30-300 microballoon, 0.75 g Aluminum chloride anhydrous and the 0.40 g aluminium powder of the disclosed technical scheme preparation of Chinese invention patent CN101186661 in advance in the there-necked flask of exsiccant 250 mL.The carbon tetrachloride solvent that adds 75 mL and stirs UniPS 30-300 microballoon in there-necked flask.At last, slowly drip bromine chloride 25 mL in above-mentioned aaerosol solution, about 30 min dropwise.Reaction is controlled and is washed the ball step with embodiment 1.Obtain exsiccant polymer microsphere 20.60 g, bromine content is 51.46%.
Embodiment 3
Reaction unit and tail gas absorb identical with embodiment 1.Weighing 10.00 g press PS UniPS 30-300 microballoon, 0.40g Aluminum chloride anhydrous, 0.20 g aluminium powder and the anhydrous Vanadium Pentoxide in FLAKES of 0.50g of the disclosed technical scheme preparation of Chinese invention patent CN101186661 in advance in the there-necked flask of exsiccant 250 mL.Elder generation adds the chloroform solvent of 50 mL in there-necked flask, and microballoon is stirred.Slowly drip bromine 50 mL in above-mentioned aaerosol solution, about 30 min dropwise, and slowly are warming up to 35 ℃ to guarantee reacting balance, and reaction is spent the night.Wash the ball step also with embodiment 1.Obtain exsiccant polymer microsphere 21.35 g, bromine content is 53.16%.
Claims (5)
1. polymer microsphere, it is basic ball with PS, it is characterized in that: said basic ball surface is contained with soccerballene and is produced the interactional bromobenzene ring structure of π-π; Described bromobenzene ring structure is replaced by bromine atoms by the Wasserstoffatoms on the contained phenyl ring of basic ball and obtains.
2. the preparation method of a polymer microsphere as claimed in claim 1 is characterized in that comprising the steps:
(1) be that 10～40 μ m, monodispersed polystyrene microsphere are basic ball with particle diameter, after catalyst mix, add the aliphatic halogenated hydrocarbon kind solvent, agitation condition slowly drips bromizating agent down; By weight, the ratio of basic ball and solvent is 1:10～15, the ratio of basic ball and bromizating agent is 1: 4.7～7.8; Described catalyzer is reduction Fe powder, or reduction Al and AlCl
3Mixture, wherein, Al and AlCl
3Ratio be 1: 1～2; The ratio of base ball and catalyst reduction Fe powder is 1: 0.05～0.10, basic ball and catalyst A l and AlCl
3The ratio of mixture be 1: 0.06～0.11;
(2) slowly be warming up to 35～50 ℃ and carry out substitution reaction; After reaction finishes, aaerosol solution is reduced to room temperature, add basic soln and carry out neutralization reaction, take out microballoon again,, obtain a kind of polymer microsphere through washing, drying.
3. the preparation method of a kind of polymer microsphere according to claim 2 is characterized in that: described aliphatic halogenated hydrocarbon kind solvent is a kind of in methylene dichloride, chloroform, tetracol phenixin, the ethylene dichloride or their arbitrary combination.
4. the preparation method of a kind of polymer microsphere according to claim 2 is characterized in that: described bromizating agent is a kind of or combination in bromine, the bromine chloride.
5. the application of a polymer microsphere as claimed in claim 1 is characterized in that: being used for moving phase is the isolating liquid chromatography stationary phase of soccerballene of toluene or o-Xylol.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863640A (en) * | 2012-10-11 | 2013-01-09 | 苏州大德碳纳米科技有限公司 | Polymer microsphere preparation method and polymer microsphere application |
| CN104276564A (en) * | 2014-10-29 | 2015-01-14 | 苏州纳微科技有限公司 | Application of carbonized microspheres |
| CN104275152A (en) * | 2014-10-29 | 2015-01-14 | 苏州纳微科技有限公司 | Carbonized micro-ball and preparation method thereof |
| CN108794670A (en) * | 2017-05-03 | 2018-11-13 | 中国石油天然气股份有限公司 | The method of improved synthesizing poly alpha-olefin base oil |
Citations (1)
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|---|---|---|---|---|
| CN101497673B (en) * | 2009-02-20 | 2011-01-05 | 淮海工学院 | Process for preparing brominated polystyrene |
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2012
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497673B (en) * | 2009-02-20 | 2011-01-05 | 淮海工学院 | Process for preparing brominated polystyrene |
Non-Patent Citations (1)
| Title |
|---|
| 胡玉玲等: "色谱法分离纯化富勒烯的研究进展", 《化学通报》, no. 3, 31 March 2001 (2001-03-31), pages 141 - 145 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863640A (en) * | 2012-10-11 | 2013-01-09 | 苏州大德碳纳米科技有限公司 | Polymer microsphere preparation method and polymer microsphere application |
| CN102863640B (en) * | 2012-10-11 | 2013-10-16 | 苏州大德碳纳米科技有限公司 | Polymer microsphere preparation method and polymer microsphere application |
| CN104276564A (en) * | 2014-10-29 | 2015-01-14 | 苏州纳微科技有限公司 | Application of carbonized microspheres |
| CN104275152A (en) * | 2014-10-29 | 2015-01-14 | 苏州纳微科技有限公司 | Carbonized micro-ball and preparation method thereof |
| CN104276564B (en) * | 2014-10-29 | 2016-08-24 | 苏州纳微科技有限公司 | A kind of application of carbonization microsphere |
| CN108794670A (en) * | 2017-05-03 | 2018-11-13 | 中国石油天然气股份有限公司 | The method of improved synthesizing poly alpha-olefin base oil |
| CN108794670B (en) * | 2017-05-03 | 2020-11-06 | 中国石油天然气股份有限公司 | Improved process for synthesizing polyalphaolefin base oils |
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| CN102659966B (en) | 2016-07-06 |
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Address after: No. 2, Bai Sichuan street, Suzhou Industrial Park, Jiangsu Province Patentee after: Suzhou Nanwei Polytron Technologies Inc Address before: 215123 bio nano technology park 218, Xing Hu Street, Suzhou Industrial Park, Suzhou, Jiangsu C1-A Patentee before: SUZHOU NANOMICRO TECHNOLOGY COMPANY LIMITED |