CN85100893A - The semi-hydrophilic double cross linked polymer porous microbeads chromatograph packing material - Google Patents
The semi-hydrophilic double cross linked polymer porous microbeads chromatograph packing material Download PDFInfo
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- CN85100893A CN85100893A CN 85100893 CN85100893A CN85100893A CN 85100893 A CN85100893 A CN 85100893A CN 85100893 CN85100893 CN 85100893 CN 85100893 A CN85100893 A CN 85100893A CN 85100893 A CN85100893 A CN 85100893A
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- filler
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Abstract
The invention belongs to the semi-hydrophilic macromolecule porous microsphere chromatogram filler.
A kind of semi-hydrophilic double cross linked polymer type chromatograph packing material---the porous microsphere of Ethylene glycol dimethacrylate and divinylbenzene crosslink copolymerization that is synthesized has the thermal stability height, and physical strength is big, characteristics such as good and highly versatile of chromatogram selectivity.With the different grain size fraction of a collection of sintetics, can be respectively applied for and separate lower fatty acid, alcohol etc. in the gas chromatography; Separating water-soluble vitamin in the high performance liquid chromatography, biochemical substances such as nucleic acid base and some water miscible medicine etc.; Measure the molecular weight distribution of water soluble polymer and oil-soluble polymer in the volume removing chromatogram.
Description
The field is the semi-hydrophilic macromolecule porous microsphere chromatogram filler under the present invention
The technical background and the present situation of semi-hydrophilic macromolecule porous microsphere chromatogram filler are as follows:
Porous polymer bead has good selectivity as chromatograph packing material, bigger column capacity and pH value usable range widely.Thereby developed rapidly, and in all kinds chromatogram (comprise gas phase, high performance liquid chromatogram, volume are got rid of and ion-exchange etc.) technology relevant extensive use.Present macromolecule type chromatograph packing material in the international market mainly contains the product of states such as U.S., day.Because filler is the core of chromatographic technique, external general how research in the exploitation laboratory of enterprise is so the preparation method strictly maintains secrecy.Containing the esters of acrylic acid group, the high molecular porous microsphere of certain hydrophilicity is arranged, is an important class chromatograph packing material, existing abroad more report and patent.The Chromosorb 107(of the gas chromatography aspect such as the U.S. is suitable for the separation of some polar compound); The Hitach Gel 3020 of high performance liquid chromatography aspect such as Japan, (being suitable for separating some water soluble compound) such as the XAD-7 of the U.S.; (being suitable for the separation of water soluble polymer) such as the Sphoron P of the TSK-GEL-PW of volume removing chromatogram aspect such as Japan, Czech, these fillers all have certain representativeness.But up to now, do not see existing good chromatographic performance as yet, the report of the filler of versatility is arranged again.
Purpose of the present invention:
The porous microsphere of Ethylene glycol dimethacrylate that the present invention is prepared and divinylbenzene crosslink copolymerization, as universal chromatograph packing material, be respectively applied for gas chromatography (separating organic acid and pure isopolarity compound), high pressure liquid chromatography (separating some water-soluble biochemical substances) and volume removing chromatogram (measuring water-soluble and molecular weight oil-soluble polymer) by its particle size range.
Technology of the present invention constitutes:
1. the present invention is to be that raw material, azoisobutyronitrile are initiating agent with Ethylene glycol dimethacrylate and divinylbenzene, the inert solvent that mixes is a pore-foaming agent, and the method for employing suspension polymerization prepares the copolymerzation with cross-linking porous polymer bead of semi-hydrophilic in aqueous media.The employed two kinds of raw materials of polymerization all can play crosslinked action.The polymer carrier of this double cross connection degree of swelling in different solvents changes very little, is convenient in use change solvent; The thermal stability height, physical strength is big, is convenient at temperature height (in 350 ℃), the big (300Kg/cm of pressure
2Below) condition under use.In chromatographic technique, the granularity of filler is one of principal element that influences column efficiency, and in high molecular suspension polymerization technique, grain size is mainly determined by dispersed system, feedstock property (monomer and thinning agent) and stirring rate.Desire prepares the microballoon of suitable particle size range, and considers the factors such as complexity that raw material, thinning agent character are eliminated after polymerization is finished the influence and the stabilizing agent of balling-up process.The present invention has selected gelatin-magnesium carbonate compound dispersing agent.The prepared filler sphere of this system is complete, granularity suitable, narrow distribution range, and any surface finish is convenient to clean the product yield height.
2. the present invention adopts the method for solvent pore, makes high polymer micro balloons obtain the structure of porous.Porous structure not only can improve the chromatogram capacity of filler, and can obviously influence the dynamic behavior in the chromatogram mass transport process.For volume removing chromatogram, the porous structure of filler is the superpolymer basis of relying and separating especially then.The selection of pore thinning agent except considering to react with raw material, can fully be dissolved each other with raw material and polyreaction can also need be considered the hole that can make specific dimensions size and structural form to be fallen etc. outside the necessary condition by extracting easily after finishing.Though inert solvent does not participate in reaction, play solvent action in the polymerization process and make the configuration difference of chain growth.Especially be easy to generate the work that is separated in the crosslinked polymerization of height, its degree is with solvent property and dosage and different.It is generally acknowledged that the poor solvent of inertia can make bigger hole, but must consider its solvability as thinning agent.In the poor solvent medium, macromolecule just precipitates prior to gelation point, forms the superpolymer of non-homogeneous state, has just stayed permanent hole after solvent is by extracting.It is to reduce with the swellbility of macromolecule microbeam in oil phase to increase, and also increases with the increase that is filled quantity of solvent between microbeam simultaneously.It is poor solvent that the present invention has adopted the potpourri of toluene-white oil, uses isoamylol to regulate and carries out pore.Mensuration by structural parameters and chromatographic performance shows the purpose that has reached the phase of giving.
3. the present invention is with a collection of synthetic porous polymer microballoon, behind carrying out washing treatment and solvent extraction, carries out classification of sedimentation in water.Can add small amount of ethanol and regulate in order to quicken sedimentation.By the granule size of institute's classification, provide gas phase, high performance liquid chromatogram and volume removing chromatogram to use respectively.
Six, effect
The prepared linked polymer porous microballoon of semi-hydrophilic double cross of the present invention has the selectivity height as chromatograph packing material, highly versatile, characteristics such as column capacity is big, and the pH value usable range is wide, high temperature resistant, high pressure resistant.In gas chromatography, can be used for the separation of samples such as scabrous fatty acid; In high performance liquid chromatography, can be used for separating of water-soluble biochemical substances and water soluble vitamin, nucleic acid base and some drugs; In volume removing chromatogram, can be used for water-soluble and oil-soluble molecular weight polymeric Determination of distribution.
Seven, specific embodiment
Synthesizing of example 1 filler
DVB 6 grams
EGDM 9 grams
White oil-toluene-iso pentane alcohol mixture 17 grams
AIBN 0.2 gram
MgCO
35 grams
In the reaction bulb of stirring is housed, be medium with water, 70 ℃ were carried out suspension polymerization 24 hours.With the centrifuging of gained high polymer micro balloons, handle and wash with water with watery hydrochloric acid repeatedly.Remove pore-foaming agent with the extracting of acetone equal solvent, classification then.
The test of example 2 chromatographic performances
1. gas chromatography performance
Instrument: Perkin Elmer F-17 FID
Pillar: φ 3.6 * 450mm, filling granularity is the filler of 30-100 μ m
Flow velocity: (H
2) the 30ml/ branch, 145 ℃ of column temperatures
Can make biased sample formic acid (123 "), acetate (143 "), propionic acid (286 ")
Butyric acid (well separated by 545 ") etc.; Also can make biased sample methyl alcohol (44 ")
Ethanol (72 "), n-propanol (157 "), normal butyl alcohol (394 "), just
Amylalcohol (well separated by 836 ").
2. high pressure liquid chromatography performance
Instrument: Hitach; 635, UV254
Pillar: φ 2.6 * 500mm, filling granularity is 15-25 μ m filler
Use 7.5%C
2H
5OH-0.05M Tris HCl, the 05ml/ branch, 15 ℃ condition can make nucleic acid base C, G, A, T be separated.
Use 10%CH
3OH-0.05M(KH
2PO
4-Na
2HPO
412H
2O) 1ml/ branch, 50 ℃ condition can make water-soluble (vitamin) B
6, B
1, B
2Deng being separated.
Use 5%C
2H
5OH-0.05M Tris HCl 2.5ml/ branch, 15 ℃ bar can make alanine, 7-ADCA be separated.
Use 5%C
2H
5OH-005M Tris HCl 2.5ml/ branch, 15 ℃ condition can make 5-Fu fluorouracil, FT-207 Fluorofur be separated.
3. volume removing chromatogram performance
Be leacheate with the tetrahydrofuran on high pressure liquid chromatograph, polystyrene is a standard, can obtain the water-soluble molecular weight-elution volume calibration curve of filler; NaN with 0.02%
3Aqueous solution is a leacheate, and glucosan is a standard, can obtain the water-soluble molecular weight-elution volume calibration curve of filler.The porous polymer bead that is synthesized all can reach request for utilization as the filler of two kinds of volume removing chromatograms.
Claims (5)
1, a kind of macromolecule porous microsphere chromatogram filler is characterized in that the universal chromatographic column filler (being applicable to gas phase, high performance liquid chromatogram and volume removing chromatogram) for the linked polymer porous microballoon of a kind of semi-hydrophilic double cross.It is decomposing (than existing procucts good heat resistance), resistance to pressure at 300kg/cm more than 350 ℃
2More than little, the highly versatile (be suitable for three kinds of chromatograms with a collection of sintetics and use, and characteristic is respectively arranged) of (being higher than existing procucts), the degree of swelling in different solvents.
2, macromolecule porous microsphere chromatogram filler as claimed in claim 1, it is characterized in that the linked polymer porous microballoon of semi-hydrophilic double cross is is that raw material, AIBN are initiating agent with Ethylene glycol dimethacrylate and divinylbenzene, in aqueous media, carry out suspension polymerization and make.Polymerization product is adjusted in classification in the water with small amount of ethanol, is provided in different chromatograms with the granularity difference and uses.
3, a kind of method for making of macromolecule porous microsphere chromatogram filler is characterized in that adopting compound dispersing agent and mixed solvent hole forming technology in polymerization process, and control is synthetic and the classification condition, makes product reach performance requirement.
4, the method for making of macromolecule porous microsphere chromatogram filler as claimed in claim 3 is characterized in that it is gelatin-magnesium carbonate that used composite dispersion amasss, and with suitable raw material proportioning and stirring rate, makes the shape of product of gained and granularity reach requirement.
5, as claim 3, the method for making of 4 described macromolecule porous microsphere chromatogram fillers is characterized in that employed mixed solvent, and promptly toluene-whiteruss potpourri is non-good agent, and regulate with isoamylol and to cause gift, make the product of made porous structure reach performance requirement.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100893A CN85100893B (en) | 1985-04-01 | 1985-04-01 | Chromatographic packing material with semi-hydrophilic double cross linked polymer porous microbeads |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100893A CN85100893B (en) | 1985-04-01 | 1985-04-01 | Chromatographic packing material with semi-hydrophilic double cross linked polymer porous microbeads |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85100893A true CN85100893A (en) | 1986-08-27 |
| CN85100893B CN85100893B (en) | 1986-10-29 |
Family
ID=4791508
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85100893A Expired CN85100893B (en) | 1985-04-01 | 1985-04-01 | Chromatographic packing material with semi-hydrophilic double cross linked polymer porous microbeads |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85100893B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107255683A (en) * | 2017-07-05 | 2017-10-17 | 中国人民解放军63605部队 | A kind of hydrazine propellant analysis filling column preparation method |
| CN108531563A (en) * | 2018-02-05 | 2018-09-14 | 深圳市尚维高科有限公司 | The purposes and lysate of porous microsphere and the application method of lysate |
-
1985
- 1985-04-01 CN CN85100893A patent/CN85100893B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107255683A (en) * | 2017-07-05 | 2017-10-17 | 中国人民解放军63605部队 | A kind of hydrazine propellant analysis filling column preparation method |
| CN108531563A (en) * | 2018-02-05 | 2018-09-14 | 深圳市尚维高科有限公司 | The purposes and lysate of porous microsphere and the application method of lysate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN85100893B (en) | 1986-10-29 |
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