CN1043146C - Method for mfg. fixed phase of high efficiency liquid phase chromatogram for separating fulvene - Google Patents
Method for mfg. fixed phase of high efficiency liquid phase chromatogram for separating fulvene Download PDFInfo
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- CN1043146C CN1043146C CN94119427A CN94119427A CN1043146C CN 1043146 C CN1043146 C CN 1043146C CN 94119427 A CN94119427 A CN 94119427A CN 94119427 A CN94119427 A CN 94119427A CN 1043146 C CN1043146 C CN 1043146C
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- pore
- ball
- toluene
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Abstract
The present invention relates to a manufacturing method for a fixed phase of high efficiency liquid chromatogram for separating fulvene. The fixed phase can use 0-xylene as a mobile phase to separate C60, C70 and high carbon fulvene. A macroporous polystyrene-divinyl benzene radical group is prepared from styrene as a raw material and divinylbenzene as a crosslinking agent by a suspension polymerization method in the presence of a pore-forming material in a dispersion system; then the radical group is chemically modified; 2-(3, 4 xylyl) ethyl whose acting force is strong to the molecules C60 and C70 is used as a separation functional group to be connected to the radical group. The fixed phase provided by the present invention has high column capacity and is particularly suitable for the mass preparation and separation of C60 and C70 with high purity.
Description
The present invention relates to a kind of manufacture method that is used for the isolating high performance liquid chromatography stationary phase of soccerballene.
This stationary phase can be the moving phase separation of C with O-dimethylbenzene
60, C
70And higher fullerene.Because of C
60, C
70Big Deng solubleness in O-dimethylbenzene, and C
60, C
70Separation factor height in this system, thereby column capacity is big, is particularly suitable for high-purity C
60, C
70Deng preparation separate.The invention belongs to the macromolecular compound technical field.
Nineteen ninety Kraetschmer and Huffman etc. have reported and can prepare C in a large number in arc process under the inert atmosphere
60, C
70And the compound of higher carbon number, be generically and collectively referred to as soccerballene (Fullerenes).Soccerballene has distinctive molecular structure and physicochemical property.C
60Be the compound of the football shaped of hollow, can produce superconducting property at the inner different elements that mix of its molecular ball, soccerballene has very strong electron acceptability, and good nonlinear optical property is expected to play a significant role in high-tech sector.Thereby the research of relevant soccerballene has become one of subjects such as international physics, chemistry, material very active research field.Yet the soluble substance that is extracted from the cigarette ash of arc process preparation by benzene or toluene is the mixture of soccerballene, mainly contains C
60, C
70, ratio is approximately 75: 25-85: between 15, also have the soccerballene (hereinafter to be referred as higher fullerene) of small amount of carbon atomicity greater than 70 higher carbon number.From fullerene mixture, separate the pure C of preparation
60And C
70Or higher fullerene is a very difficult job.It is stationary phase that aluminum oxide is adopted in present many laboratories, and oneself separates soccerballene for the moving phase chromatography by intact/toluene (95: 5) n-.Soccerballene solubleness in hexane is too low, only be the μ g/ml order of magnitude, and solubleness is bigger in toluene, O-dimethylbenzene, reaches 3.5mg/ml and 11mg/ml respectively.But with toluene or O-dimethylbenzene is moving phase, C
60And C
70On post, do not keep and can't separate.C in addition
60, C
70Also at Al
2O
3Irreversible adsorption on the post, so that C
60, C
70Can not quantitative recovery, and Al after the flash liberation
2O
3Promptly by C
60, C
70Pollute and can not use repeatedly.Like this, separate the pure C of 1g
60Need 10KgAl approximately
2O
3With the 50L solvent, need the 16-20h disengaging time.The Graphite Powder 99 post, 3, it is moving phase that 5-dinitrophenyl modified silica-gel post (being called the Pirkle post) or 3,5-dinitraniline propyl group modified silica-gel post etc. all need with hexane, with Al
2O
3There is similar problem in post, all can't prepare pure C in a large number
60, C
70Gel chromatographic columns Ultrastyragel (U.S. Waters company) can use toluene to be the moving phase separation of C
60And C
70, because of C
60, C
70Solubleness is bigger in toluene, and separation efficiency is greatly improved.But gel chromatographic columns is to C
60, C
70Separation factor not high, C when sample size is not very big
60With C
70Serious giving birth to just taken place at the peak folds.Cause the preparation separation condition under peak purity not high, column capacity is low.Someone adds methyl chloride in moving phase, changed resolution, but the adding of methyl chloride reduces C
60, C
70Solubleness in moving phase is not so total column capacity is improved.
As seen by above-mentioned, the preparation of high purity soccerballene at present separates and still has certain difficulty, and it directly influences the extensive theory and the applied research of soccerballene.
The objective of the invention is to prepare a kind of high performance liquid chromatography stationary phase.The high performance liquid chromatography that it can be used for soccerballene separates.Can select for use than strong solvent O-dimethylbenzene is moving phase, because of C
60, C
70Solubleness is high nearly three times in than toluene in O-dimethylbenzene, simultaneously C
60, C
70Separation factor in this chromatogram system is high on than gel chromatographic columns, thereby total column capacity is higher tens times than gel column.This post also has the advantage that is difficult for the absorption soccerballene, and post can use repeatedly.Post is imitated also than higher, is up to now the best soccerballene parting material.Be particularly suitable for high-purity C
60, C
70Mass preparation separate.
The manufacture method that is used for the isolating high performance liquid chromatography stationary phase of soccerballene of the present invention's research may further comprise the steps:
(1) preparation macroporous polystyrene-divinyl phenyl ball:
A, water are formed:
Dispersion agent and the tensio-active agent of concentration more than micelle-forming concentration that the water weight percent concentration is 0.1-5% are soluble in water with accounting for, become water, dispersion agent wherein is gelatin or polyvinyl alcohol, and tensio-active agent is sodium lauryl sulphate or Volpo S 10;
B, organic phase are formed:
With vinylbenzene is raw material, divinylbenzene is that linking agent is mixed into monomer, degree of crosslinking is the 8-50% divinylbenzene, add initiator and pore-creating agent then, add-on is: monomer: initiator=1: 0.5-2, and monomer: pore-creating agent=1: 0.3-1.5, initiator wherein are benzoyl peroxide or Diisopropyl azodicarboxylate, pore-creating agent is toluene and n-undecane, and toluene proportion in pore-creating agent is 10-100%;
C, with organic phase: the ratio of water=1: 10-20 is scattered in water with above-mentioned organic phase, under 70-85 ℃ temperature, stirs fast, reacts 15-20 hour, makes macroporous polystyrene-divinyl phenyl ball R-H;
(2) basic ball is carried out chemically modified:
A, with basic ball: catalyzer=1: 1～3, basic ball: 1, the ratio of 2-ethylene dichloride=1: 2～9 adds catalyzer and 1 in basic ball, the 2-ethylene dichloride, under 50～90 ℃, violent stirring react 10～50 minutes then, must R-CH
2-CH
2Cl resin, catalyzer wherein are anhydrous AlCl
3
B, with R-CH
2-CH
2Cl: anhydrous AlCl
3=1: 1～3, R-CH
2-CH
2Cl: the ratio of 0-dimethylbenzene=1: 2～9, at R-CH
2-CH
2Add anhydrous AlCl among the Cl
3With O-dimethylbenzene, under 50～90 ℃, violent stirring was reacted 10-50 minute then;
(3) carrying out washing treatment:
With above-mentioned second resin that obtains, add hydrochloric acid soln, wash, with the excessive AlCl of flush away
3, use toluene and acetone repetitive scrubbing, suction filtration, drying again, promptly get the high performance liquid chromatography stationary phase, i.e. 2-(3, the 4-xylyl) the modified macroporous polystyrene-divinylbenzene resin of ethyl stationary phase.
The present invention at first prepares macroporous polystyrene-divinylbenzene copolymer base ball with suspension polymerization, starts with from molecular structure and Intermolecular Forces analysis again, has the polymkeric substance stationary phase that certain separation function is rolled into a ball by the chemical modification method preparation.With this stationary phase separation of C
60, C
70Obtain good separating effect.
Macroporous polystyrene of the present invention-divinylbenzene copolymer base ball is to be that raw material, divinylbenzene are linking agent with vinylbenzene, the two common compositing monomer.In the presence of pore-creating agent, prepare by suspension polymerization.
Be to obtain ideal chromatogram dynamic performance, can by select suitable synthesis condition with the basic ball of preparation appropriate well structure should the base ball mean pore size be 100-500A, granularity is 8-15 μ m.Change the amount of linking agent when synthetic to change the degree of crosslinking of basic ball.The degree of crosslinking of base ball is in the 8-50% scope, preferably in the 20-45% scope.The stationary phase that degree of crosslinking makes when too low swelling in solvent is more serious, and too high then separating effect is not good.The adding pore-creating agent can increase the aperture and the pore volume of resin matrix.Pore-creating agent is mixed by a certain percentage with the n-undecane by toluene and forms.Pore-creating agent and monomeric ratio are (0.3-1.5): 1, and toluene shared ratio in pore-creating agent is 10-100%, is preferably between the 30-95%.The toluene ratio is low, and the resin aperture is too big and specific surface area is little, and post is imitated low.The toluene ratio is too high, and then the aperture is little and resistance to mass transfer is big.Reaction also need add radical initiator.The present invention can select for use benzoyl peroxide, Diisopropyl azodicarboxylate etc. to make initiator.The amount of initiator is monomeric 0.5-2%, more than forms organic phase.
Be reflected in the suitable dispersion system and finish.Dispersion system is the water that contains dispersion agent, tensio-active agent.The optional gelatin of dispersion agent, polyvinyl alcohol etc.Dispersion agent is 0.1-5% (weight ratio) in the concentration of aqueous phase.Also need add proper amount of surfactant in the dispersion system in addition.Anions selected tensio-active agent such as sodium lauryl sulphate or non-ionic surfactant polyoxyethylene alcohol.Surfactant concentration is more than micelle-forming concentration.Organic phase is 1 with the volume ratio of water: (10-20).Temperature of reaction is between 70-85 ℃.Entire reaction is carried out under stirring fast, and the reaction times is 15-20h.Make macroporous polystyrene-divinyl phenyl ball (following represent) like this with R-H.
Chemically modified be with C
60, C
70The stronger chemical group of Intermolecular Forces receives by chemical reaction that basic ball gets on.The present invention selects 2-(3, the 4-xylyl) ethyl for use.
Base group modification adopts two step Friedel-Crafts reactions, that is, the first step is at a certain temperature with anhydrous AlCl
3Be catalyzer, with 1, the 2-ethylene dichloride is for connecting bridge, with basic ball reaction, general-CH
2CH
2The Cl radical reaction is connected on the basic ball, makes R-CH
2-CH
2The Cl resin.Such resin still can not separate C
60And C
70Second step is with anhydrous AlCl
3Be catalyzer, again with R-CH
2-CH
2The Cl resin
With the reaction of O-dimethylbenzene, preparation
Resin,
This resin is called 2-(3, the 4-xylyl) ethyl modified polystyrene-divinylbenzene resin, can be with C
60, C
70Effectively separately.
Add excessive ethylene dichloride in the first step reaction, so that the topped amount of modification group is big as far as possible.The weight ratio of base ball and ethylene dichloride is 1: 2-1: 9, and basic ball and AlCl
3Weight ratio be 1: 1-1: O-dimethylbenzene then is excessive in 3, the second step reactions, and the ratio of resin and O-dimethylbenzene is 1: 2-1: 9, all the other react with the first step.Be reflected between 50-90 ℃ and carry out, and need violent stirring.Reaction times was at 10-50 minute.The control of temperature of reaction and time has material impact to the performance of resin, and temperature of reaction is low or the time short, and the group cover ratio is low and the separator column capacity is lower, and temperature of reaction height or overlong time easily side reaction take place and make separation not good.Reaction ends and adds 10%HCl solution with the excessive AlCl of flush away
3, with toluene or acetone repetitive scrubbing, suction filtration, drying promptly gets product.
Be the use properties of the stationary phase that further specifies preparation process of the present invention and invented, enumerate an embodiment and one below and make use-case.
Embodiment 1
In being housed, 2 liters of there-necked flasks of temperature regulator and return line add water 1400ml, add the 15g gelatin, make its dissolving under 80 ℃, be cooled to below 40 ℃, add 1% sodium lauryl sulphate 4ml, organic phase consists of: vinylbenzene 11.1ml, divinylbenzene (45%) 38.9ml, n-undecane 2.5ml, toluene 47.5ml, benzoyl peroxide 0.8g reacts 18h under stirring fast, temperature is controlled in 78 ℃, reaction finishes the back and divides the sub-cloud water, washes three to five times, and it is inferior to give a baby a bath on the third day after its birth with ethanol again, suction filtration promptly gets the macroporous polystyrene-divinyl phenyl ball about 46g of granularity between 8-15 μ m after the drying.
At 500ml band return line, in the three-necked bottle of agitator and temperature regulator, add above-mentioned resin base ball 30g, add 1,2-ethylene dichloride 180g, AlCl
3(anhydrous) 60g 85 ℃ of temperature, reacts 20min under the violent stirring, and reaction after finishing is removed heating unit, adds 200ml 10% HCl solution.Filter, wash with water repeatedly, and respectively give a baby a bath on the third day after its birth successively time with acetone, toluene, drain and in vacuum drier 80 ℃ of dry 2h, must R-CH
2-CH
2The Cl resin.
Get R-CH again
2CH
2Cl resin 30g adds-O dimethylbenzene 150g AlCl
3(anhydrous) 60g reacts 20min under 85 ℃ of violent stirring, reaction finishes the back and adds 200ml 10%HCl, and suction filtration, washing repeatedly and are respectively given a baby a bath on the third day after its birth-five times with acetone, toluene successively, get required stationary phase after the drying.
Embodiment 2
Reaction conditions is substantially with embodiment 1, but in the first step base ball preparation process, replaces gelatin with 2.0g polyvinyl alcohol (mean polymerisation degree is 1750).Tensio-active agent is selected nonionic surface active agent OP-10 for use, 2.0g, and initiator is selected Diisopropyl azodicarboxylate 1.2g for use in the organic phase, obtains the stationary phase of identical separation performance.
Make use-case 1
Getting the prepared 3.2g that fixedly makes an appointment among the embodiment 1, with the slurry method internal diameter 4.6mm that packs into, in the long 250mm stainless steel chromatogram post, on the Waters high pressure liquid chromatograph, is moving phase with O-dimethylbenzene under (14.7MPa) pressure, and flow velocity is the 0.25ml/min separation of C
60, C
70, the detection wavelength is 600nm, injects the saturated C of 0.2mlO-dimethylbenzene
60, C
70Solution obtains color atlas as shown in Figure 1.Be used on the post not retained fraction hexane measuring column dead time tro, try to achieve C
60, C
70Capacity factor k ' be respectively: 1.13,1.75.So C
60, C
70Between separation factor alpha be 1.54, in order to compare, using the UltrastyragelR of Waters company gel chromatographic columns under the same conditions (is separation of C so far
60, C
70Best pillar, 5 μ m, φ 7.8 * 300mm, aperture 500A).With O-dimethylbenzene is moving phase, 0.25ml/min, separation of C
60, C
70, C as a result
60, C
70On post, all do not keep, very fast with a unimodal outflow pillar.This illustrates stationary phase of the present invention and C
60, C
70UltrastyragelR is much better than for the intermolecular interaction force rate.And be moving phase with toluene, separation of C on the UltrastyragelR post
60, C
70The time, C
60, C
70The peak can not separate fully, there is intersection the centre, simultaneously separation factor alpha=1.31 are lower than stationary phase of the present invention, when sample size is increased to the saturated soccerballene solution of 0.8ml toluene (about 6mg), two peaks can not separate.And use stationary phase of the present invention, and on φ 4.6 * 250mm pillar, adding the saturated mixing soccerballene (about 30mg) of 2.00ml O-dimethylbenzene, two peaks still clearly separate.As seen stationary phase column capacity of the present invention is more much bigger than Ultrastyragel R post, and therefore stationary phase of the present invention is particularly useful for making the C of separating high-purity
60And C
70
Color atlas on the stationary phase post that Fig. 1 is 60, C70 makes use-case in the present invention.Wherein, post: φ 4.6 * 250mm stream, moving phase O-dimethylbenzene, flow velocity 0.25ml/min, sample introduction 0.2ml, C
60, C
70Saturated O-xylene solution detects wavelength 600nm, and first peak is C on the figure
60, second peak is C
70, numeral is a retention time on the figure, unit is min.
Claims (1)
1, a kind of manufacture method that is used for the isolating high performance liquid chromatography stationary phase of soccerballene is characterized in that this manufacture method may further comprise the steps:
(1) preparation macroporous polystyrene-divinyl phenyl ball:
A, water are formed:
Dispersion agent and the tensio-active agent of concentration more than micelle-forming concentration that the water weight percent concentration is 0.1-5% are soluble in water with accounting for, become water, dispersion agent wherein is gelatin or polyvinyl alcohol, and tensio-active agent is sodium lauryl sulphate or Volpo S 10;
B, organic phase are formed:
With vinylbenzene is raw material, divinylbenzene is that linking agent is mixed into monomer, degree of crosslinking is the 8-50% divinylbenzene, add initiator and pore-creating agent then, add-on is: monomer: initiator=1: 0.5-2, and monomer: pore-creating agent=1: 0.3-1.5, initiator wherein are benzoyl peroxide or Diisopropyl azodicarboxylate, pore-creating agent is toluene and n-undecane, and toluene proportion in pore-creating agent is 10-100%;
C, with organic phase: the ratio of water=1: 10-20 is scattered in water with above-mentioned organic phase, under 70-85 ℃ temperature, stirs fast, reacts 15-20 hour, makes macroporous polystyrene-divinyl phenyl ball R-H;
(2) basic ball is carried out chemically modified:
A, with basic ball: catalyzer=1: 1～3, basic ball: 1, the ratio of 2-ethylene dichloride=1: 2～9 adds catalyzer and 1 in basic ball, the 2-ethylene dichloride, under 50～90 ℃, violent stirring react 10～50 minutes then, must R-CH
2-CH
2Cl resin, catalyzer wherein are anhydrous AlCl
3
B, with R-CH
2-CH
2Cl: anhydrous AlCl
3=1: 1～3, R-CH
2-CH
2Cl: the ratio of 0-dimethylbenzene=1: 2～9, at R-CH
2-CH
2Add anhydrous AlCl among the Cl
3With 0-dimethylbenzene, under 50～90 ℃, violent stirring was reacted 10-50 minute then;
(3) carrying out washing treatment:
With above-mentioned second resin that obtains, add hydrochloric acid soln, wash, with the excessive AlCl of flush away
3, use toluene and acetone repetitive scrubbing, suction filtration, drying again, promptly get the high performance liquid chromatography stationary phase, i.e. 2-(3, the 4-xylyl) the modified macroporous polystyrene-divinylbenzene resin of ethyl stationary phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94119427A CN1043146C (en) | 1994-12-23 | 1994-12-23 | Method for mfg. fixed phase of high efficiency liquid phase chromatogram for separating fulvene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94119427A CN1043146C (en) | 1994-12-23 | 1994-12-23 | Method for mfg. fixed phase of high efficiency liquid phase chromatogram for separating fulvene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1108271A CN1108271A (en) | 1995-09-13 |
| CN1043146C true CN1043146C (en) | 1999-04-28 |
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ID=5039228
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94119427A Expired - Fee Related CN1043146C (en) | 1994-12-23 | 1994-12-23 | Method for mfg. fixed phase of high efficiency liquid phase chromatogram for separating fulvene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936306A (en) * | 2012-11-27 | 2013-02-20 | 辽宁大学 | Preparation method of crosslinked polystyrene resin microspheres with narrow particle size distribution |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104549184B (en) * | 2015-01-31 | 2017-02-15 | 苏州汇通色谱分离纯化有限公司 | Preparation method of special chromatography separation medium for separating fullerene and derivatives of fullerene |
| CN111266096B (en) * | 2019-09-05 | 2023-05-02 | 朱法科 | Polymer solid-phase chromatographic packing and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5281406A (en) * | 1992-04-22 | 1994-01-25 | Analytical Bio-Chemistry Laboratories, Inc. | Recovery of C60 and C70 buckminsterfullerenes from carbon soot by supercritical fluid extraction and their separation by adsorption chromatography |
-
1994
- 1994-12-23 CN CN94119427A patent/CN1043146C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5281406A (en) * | 1992-04-22 | 1994-01-25 | Analytical Bio-Chemistry Laboratories, Inc. | Recovery of C60 and C70 buckminsterfullerenes from carbon soot by supercritical fluid extraction and their separation by adsorption chromatography |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936306A (en) * | 2012-11-27 | 2013-02-20 | 辽宁大学 | Preparation method of crosslinked polystyrene resin microspheres with narrow particle size distribution |
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| Publication number | Publication date |
|---|---|
| CN1108271A (en) | 1995-09-13 |
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