CN85100893B - Chromatographic packing material with semi-hydrophilic double cross linked polymer porous microbeads - Google Patents
Chromatographic packing material with semi-hydrophilic double cross linked polymer porous microbeads Download PDFInfo
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- CN85100893B CN85100893B CN85100893A CN85100893A CN85100893B CN 85100893 B CN85100893 B CN 85100893B CN 85100893 A CN85100893 A CN 85100893A CN 85100893 A CN85100893 A CN 85100893A CN 85100893 B CN85100893 B CN 85100893B
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- soluble
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- porous microsphere
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Abstract
The present invention belongs to a semi-hydrophilic porous polymer bead microsphere chromatographic filler. A synthetic semi-hydrophilic double crosslinked polymer type chromatographic filler-a porous microsphere copolymerized by ethylene glycol dimethacrylate and divinylbenzene in a crosslinking mode has the characteristics of high thermal stability, high mechanical strength, good chromatography selectivity, high universality, etc. Different granularity grades of synthetic products of the same batch can be respectively used for the separation of lower fatty acid, alcohol, etc. in gas phase chromatography, the separation of biochemical substances of water-soluble vitamins, nucleic acid bases, etc., some water-soluble medicines, etc. in high efficiency liquid chromatography and the determination of the molecular weight distribution of water-soluble superpolymers and oil-soluble superpolymers in volume elimination chromatography.
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 (comprising gas phase, high performance liquid chromatogram, volume eliminating and ion-exchange etc.) technology, extensive use is arranged.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 porous polymer bead of certain hydrophilicity is arranged, is an important class chromatograph packing material, existing abroad more report and patent.The Chromosorb107(of the gas chromatography aspect such as the U.S. is suitable for the separation of some polar compound); The HitachGel3020 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.; The TSK-GEL-PW of volume removing chromatogram aspect such as Japan, (being suitable for the separation of water soluble polymer) such as SphoronP of 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 phase separation 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 and has reached its intended purposes.
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, handled and washed 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-17FID
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
Biased sample formic acid (123 "), acetate (143 "), propionic acid (286 ") butyric acid (545 ") etc. are well separated; Also can make biased sample methyl alcohol (44 ") ethanol (72 "), n-propanol (157 "), normal butyl alcohol (394 "), n-amyl alcohol (well separated by 836 ").
2. high pressure liquid chromatography performance
Instrument: Hitachi 635, UV254
Pillar: φ 2.6 * 500mm, filling granularity is 15-25 μ m filler
Use 7.5%C
2H
5OH 0.05MTrisHCl, the 0.5ml 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 ℃ bar can make water-soluble (vitamin) B
6, B
1, B
2Deng being separated.
Use 5%C
2H
5OH-0.05M TrisHCl0.5ml branch, 15 ℃ bar can make alanine, 7ADCA be separated.
Use 5%C
2H
5OH-0.05M TrisHCl2.5ml 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 oil-soluble molecular weight of filler, the elution volume calibration curve; 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 it being a kind of Ethylene glycol dimethacrylate of semi-hydrophilic and the divinylbenzene double cross polymers polymer microsphere of allying the communists, and its temperature tolerance can reach 350 ℃, and resistance to pressure can reach 300kg/cm
2
2, a kind of method for making of macromolecule porous microsphere chromatogram filler, it is characterized in that being is raw material with methacrylic acid glycol ester and divinylbenzene, azoisobutyronitrile is an initiating agent, in aqueous media, carry out suspension polymerization and make, polymerization product is adjusted in small amount of ethanol that classification becomes varigrained fraction in the water, uses for dissimilar chromatograms.
3, the method for making of a kind of macromolecule porous microsphere chromatogram filler as claimed in claim 2 is characterized in that polymerization process adopts compound dispersing agent and mixed solvent hole forming technology.
4, the method for making of a kind of macromolecule porous microsphere chromatogram filler as claimed in claim 3 is characterized in that employed composite dispersion is gelatin-magnesium carbonate potpourri.
5, the method for making of a kind of macromolecule porous microsphere chromatogram filler as claimed in claim 3 is characterized in that the employed mixed solvent of hole forming technology is toluene-white oil potpourri poor solvent, and uses isoamylol to regulate and carry out pore.
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 CN85100893A (en) | 1986-08-27 |
| CN85100893B true 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) |
Families Citing this family (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
Also Published As
| Publication number | Publication date |
|---|---|
| CN85100893A (en) | 1986-08-27 |
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| PB01 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| CI01 | Correction of invention patent gazette |
Correct: Deng Liru False: Deng Fengru Number: 24 Page: 70 Volume: 2 |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
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Free format text: CORRECT FROM: DENG FENG TO: DENG LINUO |
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| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |