CN1045545C - Method for preparation of high-effective fixed phase for separating C60 and C70 - Google Patents
Method for preparation of high-effective fixed phase for separating C60 and C70 Download PDFInfo
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- CN1045545C CN1045545C CN94119428A CN94119428A CN1045545C CN 1045545 C CN1045545 C CN 1045545C CN 94119428 A CN94119428 A CN 94119428A CN 94119428 A CN94119428 A CN 94119428A CN 1045545 C CN1045545 C CN 1045545C
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- dimethylbenzene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 11
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 8
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims abstract description 6
- -1 2-(3, 5-dimethylphenyl)-ethyl Chemical group 0.000 claims abstract description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 230000005526 G1 to G0 transition Effects 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- 239000012071 phase Substances 0.000 abstract description 16
- 238000000926 separation method Methods 0.000 abstract description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910003472 fullerene Inorganic materials 0.000 abstract description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 abstract description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract 2
- 238000004587 chromatography analysis Methods 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000035484 reaction time Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a preparation method for the immobile phase of modified macroporous polystyrene-divinylbenzene of the immobile phase 2-(3, 5-dimethylphenyl)-ethyl of liquid phase chromatography with high efficiency for separating fullerene. The immobile phase of the present invention is prepared by two steps of Friedel-Crafts reactions that under the condition of the existence of anhydrous AlCl3, the basal ball of a macropore polystyrene-divinylbenzene reacts with 1, 2-dichloroethane to connect a -CH2-CH2Cl basal group to the basal ball, and the basal ball reacts with m-dimethylbenzene; thereby, the immobile phase with a 2-(3, 5-dimethylphenyl)-ethyl basal group is prepared. The immobile phase can use o-dimethylbenzene as a mobile phase to efficiently separate C60 and C70, wherein the column efficiency of C60 and C70 on the immobile phase is high, and the column capacity of C60 and C70 on the immobile phase is big. The method of the present invention is particularly suitable for the separation preparation of C60 and C70 with high purity.
Description
The present invention relates to a kind of C of being used for
60, C
70The preparation method of isolating high performance liquid chromatography stationary phase belongs to the macromolecular compound technical field.This stationary phase can be moving phase high efficiency separation C with 0-dimethylbenzene
60, C
70Because of C
60, C
70Big Deng solubleness in 0-dimethylbenzene, while C
60, C
70Separation factor height in this system, thereby column capacity is big, is suitable for high-purity C
60, C
70Preparation separate.
Since C
60, C
70Since being found, scientists is extremely paid close attention to their distinctive molecular structure and physicochemical property, is expected to find in the material science of the hi-tech in future their important use.But the soccerballene by the preparation of carbon arc method is one group of mixture, wherein is mainly C
60And C
70Ratio is roughly 75: 25-85: between 15.Purifying, the pure C of separation preparation from fullerene mixture
60, C
70Be the work of a difficulty.Thereby pure C
60, C
70Price very high, be difficult to apply.With the gel chromatography stationary phase (Ultrastyragel of Waters company for example
R) separation of C
60, C
70, can use toluene to be moving phase.Separation efficiency is than Al
2O
3Deng the stationary phase height, but gel chromatographic columns is to C
60, C
70Separation factor low, peak overlapping is serious.While C
60, C
70Solubleness in moving phase toluene is not as good as high in 0-dimethylbenzene, face when being moving phase with 0-dimethylbenzene, C
60, C
70Then can not on gel chromatographic columns, separate.Thereby the column capacity of gel column is not high in preparation separates.
The objective of the invention is to prepare a kind of separation of C
60, C
70Efficient stationary phase.Prepare macroporous polystyrene-divinyl phenyl ball with suspension polymerization, have by the chemical modification method preparation again
The styrene-divinylbenzene copolymer stationary phase of functional group.To improve the stationary phase separation of C
60, C
70Separating effect.
Manufacture method of the present invention is carried out according to the following steps:
(1) preparation method of macroporous polystyrene-divinyl phenyl ball:
Selected macroporous polystyrene-divinylbenzene copolymer base the ball of the present invention is to be raw material with vinylbenzene, and divinylbenzene is a linking agent, prepares by suspension polymerization in the presence of pore-creating agent.The preparation method is summarized as follows:
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 water-soluble 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, and divinylbenzene is that linking agent prepares monomer, and degree of crosslinking is 8-50%, adds initiator and pore-creating agent then in monomer, and add-on is: monomer: initiator=1: 0.5-2%; Monomer: pore-creating agent=1: 0.3-1.5, initiator wherein are benzoyl peroxide or Diisopropyl azodicarboxylate, and pore-creating agent is the undecanoic mixture of toluene and n-, and wherein toluene accounts for the 10-100% of pore-creating agent total amount;
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, reacted 15-20 hour, make macroporous polystyrene-divinyl phenyl ball (R-H), the basic variole granularity that makes is 8-15 μ m, mean pore size 100-500A;
(2) basic ball is carried out chemically modified:
Two step Friedel-Crafts reactions are adopted in the chemically modified of basic ball, that is, the first step is in certain temperature range, with anhydrous AlCl
3Be catalyzer, with basic ball and 1, the reaction of 2-ethylene dichloride, general-CH
2-CH
2The Cl group is connected on the basic ball; In second step, this resin is reacted with m-dimethylbenzene again, with AlCl
3Be catalyzer.Make and have
The stationary phase of group.
It is excessive 1 to add in the first step reaction, and the 2-ethylene dichloride is so that the topped amount of modification group is big as far as possible.Base ball and 1, the weight ratio of 2-ethylene dichloride is 1: 2-1: 9, basic ball and AlCl
3Weight ratio be 1: 1-1: 3.Temperature of reaction is 50-90 ℃, and the reaction times is 10-50 minute.The control of temperature of reaction and time is important, and low or reaction times of temperature is short to cause the topped amount of reactive group not enough, thereby the separation capacity is low, and too high or reaction times of temperature is long to cause side reaction and separate not good.Add 10%HCl when reaction finishes removing excessive catalyzer, and with washing, organic solvent such as acetone, toluene eccysis impurity, drying is had-CH
2The resin of-CHCl group.In the reaction of second step, m-dimethylbenzene is excessive, and the ratio of resin and m-dimethylbenzene is 1: 2-5, resin and AlCl
3Ratio be 1: 1-3.Be reflected between 50-90 ℃ and carry out, and need violent stirring.Reaction times 10-50 minute.The same the first step of all the other conditions.
For the process that further specifies reaction and the separation performance of synthetic stationary phase, list an embodiment and one below and use example.
Embodiment 1
(1) macroporous polystyrene-divinyl phenyl ball preparation
Add water 1400ml in 2 liters of there-necked flasks of temperature regulator and return line are housed, add 2g polyvinyl alcohol (mean polymerisation degree is 1750), add 1% sodium lauryl sulphate 4ml, heating for dissolving is made water.Organic phase consists of: vinylbenzene 7.4ml, divinylbenzene (45%) 26.0ml, n-undecane 2.5ml, toluene 47.5ml, benzoyl peroxide 0.8g drops into water with organic phase, in 78 ℃ of reactions 18 hours, reaction was left standstill branch sub-cloud water after finishing under stirring fast, hot water wash 3-5 time, it is inferior to give a baby a bath on the third day after its birth with ethanol again, suction filtration, and getting granularity after the drying is macroporous polystyrene-divinyl phenyl ball of 8-15 μ m.
(2) basic nodularization is modified
The first step reacts in the 500ml three-necked bottle that agitator, temperature regulator and reflux condensing tube are housed, and adds 30g macroporous polystyrene-divinylbenzene copolymer base ball, adds 1,2-ethylene dichloride 180g, anhydrous AlCl
360g, return line leads to water coolant, is warming up to 85 ℃, keeps 15 minutes, and color is a scarlet.Reaction removes heating unit after finishing, and slowly adds the 300ml 10%HCl aqueous solution, and stirs.With washing repeatedly, wash for several times with acetone and toluene take out solution in glass hourglass bucket after, drying is had-CH again
2The resin of-CHCl group.
Second step reacted, and took by weighing the resin 30g of above-mentioned the first step prepared in reaction, added m-dimethylbenzene 150g, anhydrous AlCl
360g, the same the first step of all the other conditions is warming up to 85 ℃ of reactions 20 minutes, and reaction finishes the back and carries out aftertreatment with the first step same procedure, obtains having the modified macroporous polystyrene-divinylbenzene stationary phase of 2-(3, the 5-xylyl) ethyl.This stationary phase is faint yellow spherical particle.
Make use-case 1
Add o-Xylol among the synthetic stationary phase 3.5g in the above, furnishing thin pulp shape is at 150kg/cm
2During liquid method is packed the chromatographic column of φ 4.6 * 250mm under the pressure, on Waters 600 type high pressure liquid chromatographs, be moving phase with 0-dimethylbenzene, separation of C
60, C
70Column temperature is 25 ℃ of room temperatures, and the detection wavelength is 600nm, adds 0.2ml C
60, C
70Saturated 0-xylene solution, flow are 025ml/min, C
60, C
70Two peaks reach baseline separation.Therefore separating effect is fairly good.C
60And C
70The peak narrow, and the symmetry, do not find the irreversible adsorption phenomenon.When flow is reduced to 015ml/min, sample introduction 30mg C
60, C
70Biased sample, promptly during 2ml 0-dimethylbenzene saturated solution, C
60With C
70Still can obviously separate, isolating color atlas is seen Fig. 1.As seen the stationary phase that should invent is to C
60, C
70Separation efficiency very high, column capacity is very big.Roughly can predict once separable about 2-3g fullerene mixture on the preparative column of an about 50mm, the about 3h of disengaging time thus.In order to compare, we have tested the Ultrastyragel of Waters company
RPost, φ 7.8 * 300mm, 5 μ m, 500A.With toluene is moving phase, and flow is 0.15ml/min, adds 0.8ml C
60, C
70The toluene saturated solution, two peaks no longer can separate.At this moment C
60, C
70Be about 6mg, and Ultrastyragel
RThe amount of post internal fixing phase is 3.4 times of fixedly phasor of the present invention in the pillar of Fig. 1.As seen, if on the pillar of same size, stationary phase of the present invention is to C
60, C
70Column capacity be Ultrastyragel
RMore than ten times of post.
Fig. 1 makes in the use-case for the stationary phase of the present invention preparation, separates the color atlas of soccerballene.Wherein, chromatographic condition is: chromatographic column φ 4.6 * 250mm, and moving phase: 0-dimethylbenzene, flow 0.15ml/min detects wavelength: 500nm, and sample introduction: the 0-xylene solution that the 2.00ml soccerballene is saturated contains soccerballene 30mg approximately.
Claims (1)
1. manufacture method that is used for the isolating high performance liquid chromatography stationary phase of soccerballene is characterized in that this manufacture method comprises following each step:
(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 water-soluble 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, and divinylbenzene is that linking agent prepares monomer, and degree of crosslinking is 8-50%, adds initiator and pore-creating agent then in monomer, and add-on is: monomer: initiator=1: 0.5-2%; Monomer: pore-creating agent=1: 0.3-1.5, initiator wherein are benzoyl peroxide or Diisopropyl azodicarboxylate, and pore-creating agent is the undecanoic mixture of toluene and n-, and wherein toluene accounts for pore-creating agent 10-100%.
C, with organic phase: the ratio of water=1: 10-20 is scattered in water with above-mentioned organic phase, under the temperature of 70-85 ℃ of C, 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: 1,2-ethylene dichloride=1: 2～9, basic ball: anhydrous AlCl
3=1: 1～3 ratio adds 1 in basic ball, 2-ethylene dichloride and anhydrous AlCl
3Under 50～90 ℃ temperature, violent stirring was reacted 10～50 minutes then, got R-CH
2-CH
2The Cl resin;
B, with R-CH
2-CH
2Cl:m-dimethylbenzene=1: 2～5, R-CH
2-CH
2Cl: anhydrous AlCl
3=1: 1～3 ratio is at R-CH
2-CH
2Add m-dimethylbenzene and anhydrous AlCl among the Cl
3Under 50～90 ℃ temperature, violent stirring was reacted 10～50 minutes then;
(3) clean:
Resin with above-mentioned second step obtains adds hydrochloric acid soln, washs, and after washing repeatedly with toluene or acetone, suction filtration, drying promptly get the modified macroporous polystyrene-divinylbenzene stationary phase that has 2-(3, the 5-xylyl) ethyl again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94119428A CN1045545C (en) | 1994-12-23 | 1994-12-23 | Method for preparation of high-effective fixed phase for separating C60 and C70 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94119428A CN1045545C (en) | 1994-12-23 | 1994-12-23 | Method for preparation of high-effective fixed phase for separating C60 and C70 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1114656A CN1114656A (en) | 1996-01-10 |
| CN1045545C true CN1045545C (en) | 1999-10-13 |
Family
ID=5039229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94119428A Expired - Fee Related CN1045545C (en) | 1994-12-23 | 1994-12-23 | Method for preparation of high-effective fixed phase for separating C60 and C70 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1045545C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106908512B (en) * | 2017-04-06 | 2020-02-21 | 南京信息工程大学 | A method for collecting and detecting fullerenes in the atmosphere |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5296987A (en) * | 1973-10-15 | 1977-08-15 | Du Pont | Method of electrolyzing halides of alkali and*or alkaline earth metals |
| JPS626717A (en) * | 1985-07-01 | 1987-01-13 | Kobe Steel Ltd | Leveling method for continuous hot dip galvanized mild steel sheet |
| 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 CN94119428A patent/CN1045545C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5296987A (en) * | 1973-10-15 | 1977-08-15 | Du Pont | Method of electrolyzing halides of alkali and*or alkaline earth metals |
| JPS626717A (en) * | 1985-07-01 | 1987-01-13 | Kobe Steel Ltd | Leveling method for continuous hot dip galvanized mild steel sheet |
| 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 |
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| Publication number | Publication date |
|---|---|
| CN1114656A (en) | 1996-01-10 |
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