CN102863640A - Polymer microsphere preparation method and polymer microsphere application - Google Patents
Polymer microsphere preparation method and polymer microsphere application Download PDFInfo
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- CN102863640A CN102863640A CN2012103838204A CN201210383820A CN102863640A CN 102863640 A CN102863640 A CN 102863640A CN 2012103838204 A CN2012103838204 A CN 2012103838204A CN 201210383820 A CN201210383820 A CN 201210383820A CN 102863640 A CN102863640 A CN 102863640A
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Abstract
The invention discloses a polymer microsphere and preparation method and application thereof. Polystyrene is used for making a base sphere with the surface comprising a condensed-nuclei aromatic structure in pi-pi interaction with fullerene, and the structure is obtained by substituting a hydrogen atom on a benzene ring contained in the base sphere by chloromethyl and reacting with condensed-nuclei aromatics. The method includes: using a monodispersed polystyrene microsphere as the base sphere, mixing with catalyst SnCl4, adding aliphatic halogenate varsol, slowly dripping chloromethylation reagent while stirring for substitution reaction, allowing the reacted microsphere to react with the condensed-nuclei aromatics, and washing and drying the obtained microsphere to obtain a polymer microsphere with a fullerene separated liquid chromatographic stationary phase serving as a mobile phase. The preparation method of the surface modified polystyrene polymer microsphere only needs two steps, is simple in process, easy to repeat, suitable for massive production of fullerene and has the advantages of high separation efficiency and effectiveness.
Description
Technical field
The present invention relates to the macromolecular compound field, be specifically related to a kind of polystyrene polymer microsphere, preparation method and application thereof of surface modification.
Technical background
Soccerballene (Fullerene) is the full carbon molecule of hollow cage shape that a class is comprised of 12 five-rings and several six-rings, being found in the forming process of carbon dust dust in the research interplaner space in 1985, when the mass spectrum experiment of carrying out laser evaporation graphite by Kroto, Smalley and Curl, is the third homoatomic shape allosome of carbon behind diamond and graphite.Its special structure is given the performance of fullerene-based material in aspect excellences such as superconduction, magnetic, optics, catalysis.Wherein, the C that is formed by 60 carbon atoms
60-" bucky-ball " (Buckminsterfullerene) has unusual stability, and has perfect spherical symmetric structure.C
60Appearance make people recognize a brand-new carbon world, and caused immediately whole world scientist's extensive concern.1991, Huffman etc. found a kind of method that can the preparation in macroscopic quantity bucky-ball, C
60Again become the focus that each field scientist pays close attention to, and begun thus the research boom to a series of cage shape molecule-soccerballenes.Over more than 20 year, be all to have obtained significant progress in fundamental research or in practical application area.As a kind of typical carbon nano-functional material, soccerballene will play an important role in fields such as industry, national defence, the energy, scientific research, biomedicines, and wide this product of market outlook is put into national new material industry 12 planning forward position novel material-field of nanometer material technology staple product catalogues [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 usually take graphite as raw material, and product is the mixture of multiple soccerballene, wherein main component C
60And C
70Ratio greatly between 75:25 and 85:15.Because molecular structure is closely similar each other, physicochemical property are very close, and the separation and purification of product has larger difficulty.Chromatography is the effective means of present mixture separation, and it has the advantages such as good separating effect, velocity of separation be fast, demonstrates exclusive advantage in the Separation of fullerenes purifying.Particularly the chromatographic process based on charge transfer mechanism shows higher separation selectivity in the Separation of fullerenes purifying.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.Such as most of research in the world and produce the soccerballene person and use the Separation of fullerenes filler that contains pyrenyl and pentabromobenzene functional group, utilize just this interaction.But the preparation process of these silica matrix stationary phase is complicated and expensive.This filler belongs to silica matrix simultaneously, and functional group stability is limited easily, can not carry out under the condition that has alkalescence to exist in preparation and the use procedure.Particle diameter only is 5 μ m, thereby the post pressure is larger, has limited the size scale of preparation separator column, thereby has affected the output of separating, and increases use cost.Therefore, need the separating filler of a kind of with low cost and suitable extensive preparation of exploitation badly.
Chinese invention patent (CN1108271) discloses a kind of manufacture method of the Stationary Phase of HPLC for Separation of fullerenes, the macroporous polystyrene of employing-divinyl phenyl ball be take vinylbenzene as raw material, divinylbenzene is linking agent.Then will with C
60, C
70The 2-that Intermolecular Forces is stronger (3,4-xylyl) ethyl is received on the basic ball as separation function group.This stationary phase can be the moving phase separation of C with 0-dimethylbenzene
60, C
70And higher fullerene.Chinese invention patent (CN1114656) discloses a kind of Stationary Phase of HPLC 2-(3 for Separation of fullerenes, the 5-xylyl) preparation method of the modified macroporous polystyrene-divinylbenzene stationary phase of ethyl, adopt two step Friedel-Crafts reactions, 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-dimethylbenzene, makes the stationary phase with 2-(3,5-xylyl) ethyl group again.This stationary phase can be moving phase with 0-dimethylbenzene, high efficiency separation C
60And C
70But, the micro-sphere crosslinked degree of the method preparation is lower, hardness is less, easy swelling in toluene and o-Xylol, thereby post is pressed higher, thereby limited its flow velocity in chromatographic applications, it only is 0.15-0.25 mL/min that this stationary phase of 8-15 μ m allows the flow velocity of moving phase, and the preparation sample flash liberation time is more than 200 min.Existing drawbacks limit its large-scale application.Document " 2; 4; the fixedly chromatographic property research of Separation of Fullerenes of 6-trinitrophenol modification zirconium Magnesium coumpoud oxide " ([J]. chromatogram, 2005,23 (4): disclose a kind of usefulness 2 384-388.), the conduct of 4,6-trinitrophenol modification zirconium Magnesium coumpoud oxide is the method for Separation of Fullerenes fixedly.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
70Retention time be 2～4 min only, illustrate that this stationary phase is to C
60And C
70Save power a little less than, also should not prepare on a large scale the separation soccerballene.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, provide a kind of step simple, be easy to repetition, be suitable for polymer microsphere that is used for Separation of fullerenes of suitability for industrialized production and preparation method thereof.
The technical scheme that realizes the object of the invention provides a kind of polymer microsphere, and it is take polystyrene as basic ball, and the interactional condensed-nuclei aromatics structure with soccerballene generation π-π is contained on described basic ball surface; Described condensed-nuclei aromatics structure is obtained by chloromethylation group and condensed-nuclei aromatics reaction after being replaced by the chloromethylation group by the hydrogen atom on the contained phenyl ring of basic ball again.
A kind of preparation method of aforesaid polymer microsphere comprises the steps:
1, take particle diameter as 10～40 μ m, monodispersed polystyrene microsphere is as basic ball, adds the aliphatic halogenated hydrocarbon kind solvent, with catalyst S nCl
4Mix, under agitation condition, slowly drip chloromethylation reagent, slowly be warming up to 40～50 ℃ and react, obtain the chloromethylation microballoon;
2, the chloromethylation microballoon after will washing adds the aliphatic halogenated hydrocarbon kind solvent, with catalyst S nCl
4Mix, under agitation condition, add again the condensed-nuclei aromatics compound, slowly be warming up to 40～50 ℃ and react;
3, reaction complete after, aaerosol solution is down to room temperature, take out microballoon, through washing, drying, obtain a kind of polymer microsphere that produces the interactional condensed-nuclei aromatics structure of π-π with soccerballene that contains on polystyrene-based ball surface.
In technical solution of the present invention, described aliphatic halogenated hydrocarbon kind solvent is a kind of in methylene dichloride, chloroform, tetracol phenixin, the ethylene dichloride or their arbitrary combination.Described chloromethylation reagent is methylene dichloride, chloroform, tetracol phenixin, chloromethyl ether, formaldehyde-hydrochloric acid, polyoxymethylene-hydrochloric acid and Isosorbide-5-Nitrae dichloro methyl butyl ether.Described condensed-nuclei aromatics compound is pyrene, naphthalene, anthracene, Fei He guan.
By weight, the ratio of basic ball and aliphatic halogenated hydrocarbon kind solvent is 1:6～15; The ratio of base ball and chloromethylation reagent is 1:0.4～0.75; Base ball and catalyst S nCl
4Ratio be 1:0.05～0.3; The ratio of base ball and condensed-nuclei aromatics compound is 1:0.2～1.
Above-mentioned polymer microsphere provided by the present invention is applied to the Stationary Phase for HPLC that moving phase is the Separation of fullerenes of toluene or o-Xylol.
Compared with prior art, the present invention has obtained following beneficial effect:
1, the present invention is take polystyrene as basic ball, and reaction generates and can produce the interactional condensed-nuclei aromatics target product of π-π with soccerballene in hydrochloric ether, and whole reaction only needed for two steps, and step is simple, and reaction is easy to control and repeats, and suitable the amplification.
2, the micro-sphere crosslinked degree by the inventive method preparation is higher, and particle diameter is large, and hardness is higher, and swelling is low in toluene and o-Xylol, and post is pressed less, thereby can use higher flow velocity, raises the efficiency.
Description of drawings
Fig. 1 is the SEM figure of the polymer microsphere of embodiment of the invention preparation;
Fig. 2 is the polymer microsphere (UniPS 30-300-pyrene) of embodiment of the invention preparation and the infrared spectra comparison diagram of polystyrene-based ball (UniPS 30-300);
Fig. 3 is that polymer microsphere with embodiment of the invention preparation is as the design sketch of stationary phase for separating of soccerballene.
Embodiment
Embodiment 1
Prepare polystyrene microsphere by the disclosed technical scheme of Chinese invention patent CN101186661, be denoted as UniPS 30-300.The polystyrene microsphere of first weighing 40.00 g in the there-necked flask of drying (UniPS 30-300 microballoon, diameter are about 30 μ m) as basic ball, adds the dichloromethane solvent of 300 mL, and microballoon is stirred, and adds 11.41 g SnCl with syringe again
4In above-mentioned aaerosol solution.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.Slowly be warming up to 50 ℃ to guarantee reacting balance, reaction is spent the night.React complete after, will react first aaerosol solution and be down to room temperature.This suspension is filtered with sand core funnel, and use acetone successively, ethanol, dilute hydrochloric acid, water, washing with alcohol microballoon, obtain dry chloromethylation polymer microsphere after the vacuum-drying and (be denoted as UniPS 30-300-CH
2Cl), be about 45.20 g.
Then, get UniPS 30-300-CH obtained above
2Cl microballoon 40g adds methylene dichloride and the 8 g pyrenes (pyrene) of 300 mL, and microballoon is stirred, and adds 11.41 g SnCl with syringe again
4In above-mentioned aaerosol solution.Slowly be warming up to 50 ℃ to guarantee reacting balance, reaction is spent the night.React complete after, will react first aaerosol solution and be down to room temperature.This suspension is filtered with sand core funnel, and use acetone successively, ethanol, dilute hydrochloric acid, water, washing with alcohol microballoon, obtain dry polymer microsphere (being denoted as UniPS 30-300-pyrene) after the vacuum-drying, be about 49.80 g.
Referring to accompanying drawing 1, it is the SEM figure by the polymer microsphere of embodiment of the invention preparation; As seen from the figure, the microspherulite diameter homogeneous belongs to mono-dispersion microballoon.
Referring to accompanying drawing 2, it is the infrared spectrogram by polymer microsphere (UniPS 30-300-pyrene) with the polystyrene-based ball (UniPS 30-300) of embodiment of the invention preparation; As seen from the figure, the microballoon after the modification obviously strengthens at the Ar-H at 3050～3100 places stretching vibration absorption peak, and the phenyl ring absorption peak at 1720～1400 places also obviously strengthens, and proves that pyrenyl is modified to phenyl ring; And 2930～2850 places-CH
2-absorb also obviously enhancing, showing has more-CH in the chloromethylation process
2-group enters microsphere surface.
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 instrument, the o-Xylol with 100% is as moving phase, and flow velocity is 1mL/min, and detecting wavelength is 310 nm, injects the soccerballene crude product that 1 mL concentration is 4.4 mg/ml.Referring to accompanying drawing 3, it be polymer microsphere with present embodiment preparation as the design sketch of stationary phase for separating of soccerballene, as seen from the figure, C
60, C
70Reach high soccerballene and realized that preparation scale separates, the separating effect of effect and Buckprep is suitable.
The diameter of the microballoon that present embodiment provides is about 30 μ m, be used as the stationary phase of liquid chromatography, because the particle of this stationary phase is larger, 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 maintenance cost of required instrument, be suitable for extensive preparation and separate soccerballene.
Embodiment 2
Reaction unit is identical with embodiment 1.Weighing 10.00 g press the polystyrene UniPS 30-300 microballoon that the disclosed technical scheme of Chinese invention patent CN101186661 prepares in advance in the there-necked flask of 250 mL of drying.Add first the chloroform solvent of 75 mL in there-necked flask, and microballoon is stirred.At last, with the SnCl that adds 2.23 g
4In above-mentioned aaerosol solution.Reaction is controlled and is washed the ball step with embodiment 1.
Chloromethylation microballoon 10.8 g obtained above with guan (coronene) 4.00 g mix, are added first the chloroform solvent of 75 mL in there-necked flask, and microballoon is stirred.At last, add 2.23 g SnCl
4In above-mentioned aaerosol solution.Reaction is controlled and is washed the ball step with embodiment 1.Get final product De Dao polymer microsphere 11.9 g of guan functionalization.
At the prepared polymer microsphere of the present invention, be to contain on polystyrene-based ball surface with soccerballene to produce the interactional condensed-nuclei aromatics structure of π-π; Described condensed-nuclei aromatics structure is obtained by chloromethylation group and condensed-nuclei aromatics reaction after being replaced by the chloromethylation group by the hydrogen atom on the contained phenyl ring of basic ball again; Condensed-nuclei aromatics refers to have in the molecular structure two above phenyl ring, and each phenyl ring has adjacent phenyl ring and share the compound fragrant hydrocarbon on a limit, also can adopt naphthalene, anthracene and the material such as luxuriant and rich with fragrance.
Claims (10)
1. polymer microsphere, it is characterized in that take polystyrene as basic ball: described basic ball surface is contained with soccerballene and is produced the interactional condensed-nuclei aromatics structure of π-π; Described condensed-nuclei aromatics structure is obtained by chloromethylation group and condensed-nuclei aromatics reaction after being replaced by the chloromethylation group by the hydrogen atom on the contained phenyl ring of basic ball again.
2. the preparation method of a polymer microsphere as claimed in claim 1 is characterized in that comprising the steps:
(1) take particle diameter as 10～40 μ m, monodispersed polystyrene microsphere is as basic ball, adds the aliphatic halogenated hydrocarbon kind solvent, with catalyst S nCl
4Mix, under agitation condition, slowly drip chloromethylation reagent, slowly be warming up to 40～50 ℃ and react, obtain the chloromethylation microballoon;
(2) the chloromethylation microballoon after will washing adds the aliphatic halogenated hydrocarbon kind solvent, with catalyst S nCl
4Mix, under agitation condition, add again the condensed-nuclei aromatics compound, slowly be warming up to 40～50 ℃ and react;
(3) reaction complete after, aaerosol solution is down to room temperature, take out microballoon, through washing, drying, obtain a kind of polymer microsphere that produces the interactional condensed-nuclei aromatics structure of π-π with soccerballene that contains on polystyrene-based ball surface.
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, it is characterized in that: described chloromethylation reagent is methylene dichloride, chloroform, tetracol phenixin, chloromethyl ether, formaldehyde-hydrochloric acid, polyoxymethylene-hydrochloric acid and Isosorbide-5-Nitrae dichloro methyl butyl ether.
5. the preparation method of a kind of polymer microsphere according to claim 2, it is characterized in that: described condensed-nuclei aromatics compound is pyrene, naphthalene, anthracene, Fei He guan.
6. the preparation method of a kind of polymer microsphere according to claim 2, it is characterized in that: by weight, the ratio of basic ball and aliphatic halogenated hydrocarbon kind solvent is 1:6～15.
7. the preparation method of a kind of polymer microsphere according to claim 2, it is characterized in that: by weight, the ratio of basic ball and chloromethylation reagent is 1:0.4～0.75.
8. the preparation method of a kind of polymer microsphere according to claim 2 is characterized in that: by weight, and basic ball and catalyst S nCl
4Ratio be 1:0.05～0.3.
9. the preparation method of a kind of polymer microsphere according to claim 2, it is characterized in that: by weight, the ratio of basic ball and condensed-nuclei aromatics compound is 1:0.2～1.
10. the application of a polymer microsphere as claimed in claim 1 is characterized in that: being used for moving phase is the Stationary Phase for HPLC of the Separation of fullerenes of toluene or o-Xylol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106633733A (en) * | 2017-01-04 | 2017-05-10 | 青岛科技大学 | Preparation method of fullerene square lamellar crystal/polymer composite material |
| CN108997820A (en) * | 2018-07-25 | 2018-12-14 | 华南师范大学 | A kind of dyestuff microballoon and preparation method thereof, ink and electric moistening display part |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800005A (en) * | 2005-11-03 | 2006-07-12 | 福建师范大学 | High carbon fullerene preparation method |
| CN102659966A (en) * | 2012-04-13 | 2012-09-12 | 苏州纳微生物科技有限公司 | Polymer microsphere, preparation method and application thereof |
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2012
- 2012-10-11 CN CN 201210383820 patent/CN102863640B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800005A (en) * | 2005-11-03 | 2006-07-12 | 福建师范大学 | High carbon fullerene preparation method |
| CN102659966A (en) * | 2012-04-13 | 2012-09-12 | 苏州纳微生物科技有限公司 | Polymer microsphere, preparation method and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106633733A (en) * | 2017-01-04 | 2017-05-10 | 青岛科技大学 | Preparation method of fullerene square lamellar crystal/polymer composite material |
| CN108997820A (en) * | 2018-07-25 | 2018-12-14 | 华南师范大学 | A kind of dyestuff microballoon and preparation method thereof, ink and electric moistening display part |
| CN108997820B (en) * | 2018-07-25 | 2022-01-07 | 华南师范大学 | Dye microsphere, preparation method thereof, printing ink and electrowetting display device |
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