CN105664886A - Preparation method of weak acid cation exchange stationary phase - Google Patents
Preparation method of weak acid cation exchange stationary phase Download PDFInfo
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Abstract
The invention discloses a preparation method of a weak acid cation chromatographic stationary phase with highly cross-linked glycidyl methacrylate-divinyl benzene microspheres as the matrix. The preparation method comprises the following steps: monodispersed linear polystyrene seed microspheres are prepared by a dispersion polymerization method; highly cross-linked glycidyl methacrylate-divinyl benzene copolymer microspheres are prepared by a two-step seed swelling method; and by using succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid as reaction materials, the weak acid cation chromatographic stationary phase is prepared.
Description
Technical field
The preparation method that the present invention relates to the fixing phase of a kind of chromatography of ions, specifically, is the preparation method of a kind of Weak-acid cation crossover fixation phase.
Background technology
Silica gel, as a kind of known fixing phase substrate, has stronger mechanical strength and is prone to the features such as chemical modification, has been widely used for the fixing phase system of reversed phase chromatography; But silica matrix pH tolerant is limited in scope (being generally 2-8), mobile phase Acidity of Aikalinity is restricted, hinder it and apply further. And Polymer-based Chiral stationary phase such as high cross-linked styrene-divinylbenzene organic polymer, it is possible to tolerate wider pH value range, there is relatively good mechanical strength, be widely used in the fixing phase system of chromatography of ions; Meanwhile, monodispersed micrograde polymer microsphere, as chromatograph packing material, is possible not only to reduce post pressure, it is also possible to significantly improve post effect, is especially suitable for use as the substrate of the fixing phase of chromatography of ions; Therefore, the organic polymeric microspheres tolerating broader pH value range and good mechanical strength will become the trend of chromatograph packing material substrate development. At present, high cross-linked styrene-divinylbenzene copolymerization microsphere is more as fixing phase base Quality Research report, but the research of high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere report is less. But, high cross-linked styrene-divinylbenzene copolymerization microsphere is not easy to perform the derivatization reaction, limits it and applies further; And high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere contains substantial amounts of epoxy radicals, it is easy to further derivative reaction, there is good development and application prospect.
The present invention is prepared for a kind of novel height crosslinking monodispersed glycidyl methacrylate-divinylbenzene copolymerization microsphere by Two-step seed swelling method, microsphere has good monodispersity, good mechanical strength and is prone to the characteristics such as chemical modification, is highly suitable as liquid chromatographic stationary phase filler substrate;
The present invention, with this microsphere for substrate, adopts chemical bonding to be prepared for a kind of Weak-acid cation crossover fixation phase.
Summary of the invention
The present invention is directed to the shortcoming that chromatograph packing material substrate inorganic silica gel not acid and alkali-resistance, poor chemical stability and existing high cross-linked styrene-divinylbenzene copolymerization microsphere are not easily chemically modified, it is prepared for a kind of novel tolerance acid-base, there is good mechanical strength and is prone to the high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere of chemical modification as chromatograph packing material substrate, be prepared for the Weak-acid cation chromatographic stationary phases being substrate with this microsphere simultaneously.
The present invention is achieved through the following technical solutions:
The preparation method that the invention discloses a kind of Weak-acid cation chromatographic stationary phases being substrate with high crosslinked methacrylic acid glycidyl ester-divinylbenzene microspheres, adopts dispersion copolymerization method to prepare monodispersed linear polystyrene seed microsphere; Adopt two-step seed swelling method, prepare high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere; With succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid for reaction raw materials, it is prepared for the fixing phase of a kind of weak-type cation chromatography.
As improving further, the present invention is in monodispersed linear polystyrene seed microsphere preparation process, reaction medium is ethanol water, volumetric concentration is 75～100%, and the mass concentration of monomer styrene is the 5～30% of total amount, and the quality of stabilizer polyvinylpyrrolidone is the 0.5～4% of reaction medium quality, initiator azodiisobutyronitrile quality is the 1～5% of monomer mass, reaction temperature is 40～85 DEG C, and mixing speed is 100～400r/min, and the response time is 12～24h.
As improving further, the present invention prepares in the process of high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere in two-step seed swelling method, monomer methacrylic acid ethylene oxidic ester mass concentration is the 5～40% of total organic facies, the quality of cross-linker divinylbenzene is the 10～75% of total organic facies quality, emulsifier sodium lauryl sulfate quality is the 2～4% of total organic facies quality, stabilizer polyvinyl alcohol quality is the 0.5～5% of gross mass, initiator benzoyl peroxide quality is the 0.4～1.5% of monomer mass, porogen toluene quality is the 20～70% of total organic facies quality, swelling ratio is 10～70 times, emulsifying temperature is 20～35 DEG C, reaction temperature is 60～85 DEG C, mixing speed is 100～300r/min, response time is 12～48h, the high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere particle diameter of preparation is between 6-8 μm.
As improving further, the degree of cross linking of described poly (glycidyl methacrylate)-divinylbenzene copolymerization microsphere is controlled by regulating the ratio of poly (glycidyl methacrylate) and divinylbenzene.
As improving further, the granularity of described poly (glycidyl methacrylate)-divinylbenzene copolymerization microsphere is controlled by the selection of porogen, cross-linking agent, dispersion stabilizer solubility, emulsifying temperature, reaction temperature, initiator concentration and swelling ratio.
As improving further, the present invention is in the process modifying high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere, with excessive succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid are reaction raw materials, heat 160-180 DEG C, 50-100rpm stirring reaction.
As improving further, Weak-acid cation crossover fixation prepared by the present invention fills post by homogenate method mutually, and its chromatographic performance is characterized, and is evaluated by chromatographic performance, it is possible to achieve monovalence separates with the degree drip washing such as grade of bivalent metal ion.
Present invention have the advantage that
High crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere monodispersity provided by the invention is good, and mechanical strength is high, it is possible to tolerates wider pH value range, it is easy to chemical modification, is suitable as the substrate of chromatographic stationary phases.
High crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere preparation method provided by the invention is simple and reliable;The granularity of base ball can be controlled by the selection of porogen, cross-linking agent, dispersion stabilizer solubility, swelling temperature, reaction temperature, initiator concentration and swelling ratio.
Succinic anhydride provided by the invention, phthalic anhydride, maleic anhydride and maleic acid method of modifying are simple and reliable, and cost is low, repeatable strong.
High crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere prepared by the present invention, monodispersity is good, wider relative to existing silica matrix pH tolerant scope, further derivatization easier than high cross-linked styrene-divinylbenzene copolymerization microsphere, and there is good mechanical strength, be suitable as the substrate of chromatographic stationary phases; High crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere provides substantial amounts of epoxide group, this radical reaction is strong, reaction condition is gentle, can react with multiple group single steps such as hydroxyl, amino, anhydride, widely, such method has higher feasibility and repeatability to derivatization object; The present invention realizes succinic anhydride by simple chemical method, phthalic anhydride, maleic anhydride and the maleic acid modification to high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere, show that this high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere has broad application prospects and practical application meaning as substrate.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere;
Fig. 2 is succinic anhydride, phthalic anhydride, the preparation process figure of high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere that maleic anhydride and maleic acid are modified;
Fig. 3 is that 7 kinds of cationes modify the fixing separation chromatography figure, leacheate: 5.0mmol/L gone up mutually at succinic anhydride (a), phthalic anhydride (b), maleic anhydride (d) and maleic acid (c)-1Pyrovinic acid; Suppressor conductivity detection, peak: 1, Li+; 2, Na+; 3, NH4 +4,K+5,Mg2+; 6, Ca2+; 7, Sr2+。
Detailed description of the invention
The preparation method that the present invention provides the fixing phase of a kind of Weak-acid cation exchange chromatography, including the preparation of the fixing phase of the preparation of single dispersing seed microsphere, the preparation of high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere and Weak-acid cation exchange chromatography. Concrete technical scheme is as follows:
The present invention adopts dispersion copolymerization method to prepare monodispersed linear polystyrene seed microsphere; Adopt two-step seed swelling method, prepare high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere; With succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid for modification group, introduce weak-type functional group on high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere surface; Post is filled by homogenate method; Concrete preparation process is:
A. dispersion copolymerization method is adopted to prepare monodispersed linear polystyrene seed microsphere
With styrene for monomer, polyvinylpyrrolidone is stabilizer, and azodiisobutyronitrile is initiator, ethanol and water mixed solution is reaction medium; By dispersion copolymerization method, prepare size tunable, the linear polystyrene seed microsphere that monodispersity is good;
B. two-step seed swelling method is adopted to prepare high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere
Single dispersing linear polystyrene seed microsphere is activated in dibutyl phthalate emulsion; Adding containing monomer methacrylic acid ethylene oxidic ester, cross-linker divinylbenzene, emulsifier sodium lauryl sulfate, stabilizer polyvinyl alcohol after activation, the emulsion of initiator benzoyl peroxide and porogen toluene carries out swelling;Then add thermal-initiated polymerization, prepare high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere;
C. high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere modified by succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid;
Adding in round-bottomed flask by excessive succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid and high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere, heated and stirred is reacted; Reaction terminates, and water, ethanol wash successively;
D. homogenate method dress post
Take 2.0g filler in 50mL beaker, add and high crosslinked methacrylic acid glycidyl ester-isopycnic homogenate of divinylbenzene copolymerization microsphere (water/acetonitrile mixture), ultrasonic disperse ten minutes; Being then added in packing column machine homogenate tank, with water for displacement fluid, fill post under 35MPa pressure, displacement fluid at least flows out 300mL.
Weakly strictly diagonally dominant matrix Stationary phase preparation method provided by the invention, it is with high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere for substrate, with succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid are functional group, at microsphere surface covalent bonding weak-type functional group.
Below in conjunction with accompanying drawing, by detailed description of the invention, technical scheme is described in further detail:
Embodiment 1: the making step of the fixing phase of high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere weak-type cation is:
1, first passing through dispersion copolymerization method and prepare monodisperse polystyrene seed microsphere, reaction medium is ethanol water mixed solution, and ethanol consumption is 75% (v/v); Monomer styrene consumption is 5% (m/m) of reaction medium consumption, stabilizer polyvinylpyrrolidone consumption is 0.5% (m/m) of reaction medium consumption, initiator azodiisobutyronitrile consumption is 1% (m/m) of monomer consumption, reaction temperature is 40 DEG C, mixing speed is 100r/min, response time is 12h, and the particle diameter of monodisperse polystyrene seed microsphere is about 1.8 μm;
2, prepare, by two-step seed swelling method, single dispersing height crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere that the degree of cross linking is 75%. monomer methacrylic acid ethylene oxidic ester consumption is 5% (m/m) of total organic facies consumption, cross-linker divinylbenzene consumption is 25% (m/m) of total organic facies consumption, emulsifier sodium lauryl sulfate consumption is 4% (m/m) of total organic facies consumption, stabilizer polyvinyl alcohol consumption is 5% (m/m) of total amount, initiator benzoyl peroxide consumption is 1.5% (m/m) of monomer consumption, porogen toluene consumption is 60% (m/m) of total organic facies consumption, swelling ratio is 70 times, swelling temperature is 35 DEG C, reaction temperature is 85 DEG C, mixing speed is 300r/min, response time is 12h, the high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere particle size range of preparation is between 6-8 μm, monodispersity is good, without carrying out classification and screening, response time 24h, removes porogen by polymer microballoon toluene extracting, then with water, and washing with alcohol,
3, with succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid are that functional group modifies high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere; Excessive succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid and high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere are added in round-bottomed flask, heats 160-180 DEG C, 50-100rpm stirring reaction;Reaction terminates, and water, ethanol wash successively;
4, the high crosslinked methacrylic acid glycidyl ester after succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid being modified by homogenate method-divinylbenzene filler dress post; Take 2.0g filler in 50mL beaker, add and high crosslinked methacrylic acid glycidyl ester-isopycnic homogenate of divinylbenzene copolymerization microsphere microsphere (water/acetonitrile mixture), ultrasonic disperse ten minutes; Being then added in packing column machine homogenate tank, with water for displacement fluid, fill post under 35MPa pressure, displacement fluid at least flows out 300mL.
5, with pyrovinic acid aqueous solution as mobile phase, it is suppressed that 7 kinds of cationes are detected by electric conductivity detector.
Embodiment 2: with reference to the method and steps of embodiment 1
1, first passing through dispersion copolymerization method synthesis monodisperse polystyrene seed microsphere, reaction medium is ethanol water mixed solution, and ethanol consumption is 100% (v/v); The concentration of monomer styrene is 30% (m/m) of total amount, stabilizer polyvinylpyrrolidone consumption is 4% (m/v) of reaction medium, initiator azodiisobutyronitrile consumption is 5% (m/m) of monomer consumption, reaction temperature 85 DEG C, mixing speed is at 400 revs/min, in 24 hours response time, the particle diameter of monodisperse polystyrene seed microsphere is about 1.8 μm;
2, prepare, by two-step seed swelling method, single dispersing height crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere that the degree of cross linking is 40%. seed microsphere 0.6g, the consumption of monomer methacrylic acid ethylene oxidic ester is 10% (m/m) of total organic facies consumption, cross-linker divinylbenzene consumption is 40% (m/m) of total organic facies consumption, emulsifier sodium lauryl sulfate consumption is 2.7% (m/m) of total organic facies consumption, stabilizer polyvinyl alcohol consumption is 1.5% (m/m) of total amount, initiator benzoyl peroxide consumption is 0.7% (m/m) of monomer consumption, porogen toluene consumption is 45% (m/m) of total organic facies consumption, swelling ratio is 55 times, emulsifying temperature is 20 DEG C, reaction temperature 70 DEG C, mixing speed 250r/min, response time 24h, polymer microballoon toluene extracting is removed porogen, then with water, washing with alcohol, the high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere particle size range of preparation is between 6-8 μm,
3, with succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid are that functional group modifies high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere; Excessive succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid and high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere are added in round-bottomed flask, heats 160-180 DEG C, 50-100rpm stirring reaction; Reaction terminates, and water, ethanol wash successively;
4, the high crosslinked methacrylic acid glycidyl ester after succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid being modified by homogenate method-divinylbenzene filler dress post;
Take 2.0g filler in 50mL beaker, add and high crosslinked methacrylic acid glycidyl ester-isopycnic homogenate of divinylbenzene copolymerization microsphere (water/acetonitrile mixture), ultrasonic disperse ten minutes; Being then added in packing column machine homogenate tank, with water for displacement fluid, fill post under 35MPa pressure, displacement fluid at least flows out 300mL.
5, by embodiment 1 (5) method, column chromatography performance being measured, result is consistent with 1 (5).
Embodiment 3: with reference to the method and steps of embodiment 1
1, monodisperse polystyrene seed microsphere is prepared by dispersion copolymerization method, reaction medium is 95% ethanol water, the consumption of monomer styrene is 10% (m/m) of total amount, stabilizer polyvinylpyrrolidone consumption is 1.6% (m/m) of reaction medium, initiator azodiisobutyronitrile consumption is 2.2% (m/m) of monomer consumption, reaction temperature 60 DEG C, mixing speed is 200r/min, response time is 24h, and the particle diameter of monodisperse polystyrene seed microsphere is about 1.8 μm;
2, prepare, by two-step seed swelling method, single dispersing height crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere that the degree of cross linking is 15%. seed microsphere 0.6g, the consumption of monomer methacrylic acid ethylene oxidic ester is 40% (m/m) of total organic facies consumption, cross-linker divinylbenzene consumption is 15% (m/m) of total organic facies consumption, emulsifier sodium lauryl sulfate consumption is 2% (m/m) of total organic facies consumption, stabilizer polyvinyl alcohol consumption is 0.5% (m/m) of total amount, initiator benzoyl peroxide consumption is 0.4% (m/m) of monomer consumption, porogen toluene consumption is 40% (m/m) of total organic facies consumption, swelling ratio is 25 times, emulsifying temperature is 20 DEG C, reaction temperature 60 DEG C, mixing speed 100r/min, response time 12h, polymer microballoon toluene extracting is removed porogen, then with water, washing with alcohol, the high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere particle size range of preparation is between 6-8 μm,
3, with succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid are that functional group modifies high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere; Excessive succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid and high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere are added in round-bottomed flask, heats 160-180 DEG C, 50-100rpm stirring reaction; Reaction terminates, and water, ethanol wash successively;
4, the high crosslinked methacrylic acid glycidyl ester after succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid being modified by homogenate method-divinylbenzene filler dress post;
Take 2.0g filler in 50mL beaker, add and high crosslinked methacrylic acid glycidyl ester-isopycnic homogenate of divinylbenzene copolymerization microsphere (water/acetonitrile mixture), ultrasonic disperse ten minutes; Being then added in packing column machine homogenate tank, with water for displacement fluid, fill post under 35MPa pressure, displacement fluid at least flows out 300mL.
5, by embodiment 1 (5) method, column chromatography performance being measured, result is consistent with 1 (5).
Embodiment 4: with reference to the method and steps of embodiment 1
1, monodisperse polystyrene seed microsphere is prepared by dispersion copolymerization method, reaction medium is 90% ethanol water, the consumption of monomer styrene is 25% (m/m) of total amount, stabilizer polyvinylpyrrolidone consumption is 1.6% (m/m) of reaction medium, initiator azodiisobutyronitrile consumption is 2.2% (m/m) of monomer consumption, reaction temperature 70 DEG C, mixing speed is 250r/min, response time is 24h, and the particle diameter of monodisperse polystyrene seed microsphere is about 1.8 μm;
2, prepare, by two-step seed swelling method, single dispersing height crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere that the degree of cross linking is 55%. seed microsphere 0.6g, the consumption of monomer methacrylic acid ethylene oxidic ester is 18% (m/m) of total organic facies consumption, cross-linker divinylbenzene consumption is 36% (m/m) of total organic facies consumption, emulsifier sodium lauryl sulfate consumption is 2.7% (m/m) of total organic facies consumption, stabilizer polyvinyl alcohol consumption is 1.5% (m/m) of total amount, initiator benzoyl peroxide consumption is 0.7% (m/m) of monomer consumption, porogen toluene consumption is 47% (m/m) of total organic facies consumption, swelling ratio is 55 times, emulsifying temperature is 20 DEG C, reaction temperature 70 DEG C, mixing speed 250r/min, response time 24h, polymer microballoon toluene extracting is removed porogen, then with water, washing with alcohol,, the high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere particle size range of preparation is between 6-8 μm.
3, with succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid are that functional group modifies high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere; Excessive succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid and high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere are added in round-bottomed flask, heats 160-180 DEG C, 50-100rpm stirring reaction; Reaction terminates, and water, ethanol wash (Fig. 2) successively;
4, the high crosslinked methacrylic acid glycidyl ester after succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid being modified by homogenate method-divinylbenzene filler dress post;
Take 2.0g filler in 50mL beaker, add and high crosslinked methacrylic acid glycidyl ester-isopycnic homogenate of divinylbenzene copolymerization microsphere (water/acetonitrile mixture), ultrasonic disperse ten minutes; Being then added in packing column machine homogenate tank, with water for displacement fluid, fill post under 35MPa pressure, displacement fluid at least flows out 300mL.
5, by embodiment 1 (5) method, column chromatography performance being measured, result is consistent with 1 (5).
Embodiment 5: chromatographic performance is tested
Chromatographic performance analysis is carried out mutually, it is shown that superior chromatographic isolation characteristic by utilizing 7 kinds of cationes that this is fixed.
Instrument: ICS3000 ion chromatograph
Detached dowel: 4.6 × 150mm rustless steel chromatographic column that self-made fill is loaded;
Leacheate: 5.0mmol/L-1Pyrovinic acid aqueous solution
Flow velocity: 1mL/min;
Sample: 7 kinds of cationes (1, Li+; 2, Na+; 3, NH4 +4,K+5,Mg2+; 6, Ca2+; 7, Sr2+)。
Fig. 3 is that 7 kinds of metal cations modify the fixing separation chromatography figure gone up mutually at succinic anhydride (a), phthalic anhydride (b), maleic anhydride (d) and maleic acid (c); By analysis chart 3 it can be seen that monovalence and bivalent metal ion can realize isocratic elution.
Listed above is only the some embodiments of the present invention; it is clear that the invention is not restricted to above example, it is also possible to there are many deformation; all deformation that those of ordinary skill in the art can directly derive from present disclosure or associate, are all considered as protection scope of the present invention.
Claims (7)
1. a preparation method for Weak-acid cation crossover fixation phase, is characterized in that: adopt dispersion copolymerization method to prepare monodispersed linear polystyrene seed microsphere; Adopt two-step seed swelling method, prepare high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere; With succinic anhydride, phthalic anhydride, maleic anhydride and maleic acid for reaction raw materials, prepare a kind of Weak-acid cation crossover chromatographic stationary phases being substrate with high crosslinked methacrylic acid glycidyl ester-divinylbenzene microspheres.
2. the preparation method of Weak-acid cation crossover fixation phase according to claim 1, it is characterized in that: in monodispersed linear polystyrene seed microsphere preparation process, reaction medium is ethanol water, volumetric concentration is 75～100%, the mass concentration of monomer styrene is the 5～30% of total amount, the quality of stabilizer polyvinylpyrrolidone is the 0.5～4% of reaction medium quality, initiator azodiisobutyronitrile quality is the 1～5% of monomer mass, reaction temperature is 40～85 DEG C, mixing speed is 100～400r/min, and the response time is 12～24h.
3. the preparation method of Weak-acid cation crossover fixation phase according to claim 1, it is characterized in that: synthesize in the process of poly (glycidyl methacrylate)-divinylbenzene copolymerization microsphere in two-step seed swelling method, monomer methacrylic acid ethylene oxidic ester mass concentration is the 5～40% of total organic facies, the quality of cross-linker divinylbenzene is the 10～75% of total organic facies quality, emulsifier sodium lauryl sulfate quality is the 2～4% of total organic facies quality, dispersion stabilizer polyvinyl alcohol quality is the 0.5～5% of gross mass, initiator benzoyl peroxide quality is the 0.4～1.5% of monomer mass, porogen toluene quality is the 20～70% of total organic facies quality, swelling ratio is 10～70 times, emulsifying temperature is 20～35 DEG C, reaction temperature is 60～85 DEG C, mixing speed is 100～300r/min, response time is 12～48h, the high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere particle diameter of preparation is between 6-8 μm.
4. the preparation method of Weak-acid cation crossover fixation phase according to claim 3, it is characterized in that: the degree of cross linking span of described poly (glycidyl methacrylate)-divinylbenzene copolymerization microsphere, between 10-75%, is controlled by regulating the ratio of poly (glycidyl methacrylate) and divinylbenzene.
5. the preparation method of Weak-acid cation crossover fixation phase according to claim 3, is characterized in that: the granularity of described poly (glycidyl methacrylate)-divinylbenzene copolymerization microsphere is controlled by the selection of porogen, cross-linking agent, dispersion stabilizer solubility, emulsifying temperature, reaction temperature, initiator concentration and swelling ratio.
6. the preparation method of Weak-acid cation crossover fixation phase according to claim 1, it is characterized in that: in the process modifying high crosslinked methacrylic acid glycidyl ester-divinylbenzene copolymerization microsphere, excessive succinic anhydride with 3-5 times of mole of microsphere, phthalic anhydride, maleic anhydride and maleic acid are reaction raw materials, without solvent and catalyst, directly heat 160-180 DEG C, 50-100rpm stirring reaction.
7. the preparation method of Weak-acid cation crossover fixation phase according to claim 1, it is characterized in that: the weak cation type of described preparation is fixing mutually with homogenate method dress post, being evaluated by chromatographic performance, monovalence is separated by display with the degree drip washing such as grade of divalent metal, it is possible to use steadily in the long term.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108276526A (en) * | 2018-01-26 | 2018-07-13 | 北京石油化工学院 | A kind of high carrying capacity large aperture polymer cation displacement chromatography medium and its preparation |
| CN109705273A (en) * | 2019-01-11 | 2019-05-03 | 青岛普仁仪器有限公司 | A kind of preparation method of Subacidity cation chromatographic column filler |
| CN112588215A (en) * | 2020-11-24 | 2021-04-02 | 北方民族大学 | Coating type cellulose high-crosslinking polymer microsphere chiral stationary phase and preparation method and application thereof |
| CN116272921A (en) * | 2023-02-15 | 2023-06-23 | 青岛盛瀚色谱技术有限公司 | Monodisperse weakly acidic cation chromatographic packing and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785225A (en) * | 2015-04-15 | 2015-07-22 | 浙江大学 | Method for preparing antiphase weak anion exchange mixed mode chromatographic stationary phase by using organic polymer as substrate |
| CN104941611A (en) * | 2015-06-02 | 2015-09-30 | 浙江大学 | Preparation method of novel grafting high-capacity dendrimer ion chromatography stationary phase stuffing |
-
2016
- 2016-01-14 CN CN201610024574.1A patent/CN105664886A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785225A (en) * | 2015-04-15 | 2015-07-22 | 浙江大学 | Method for preparing antiphase weak anion exchange mixed mode chromatographic stationary phase by using organic polymer as substrate |
| CN104941611A (en) * | 2015-06-02 | 2015-09-30 | 浙江大学 | Preparation method of novel grafting high-capacity dendrimer ion chromatography stationary phase stuffing |
Non-Patent Citations (5)
| Title |
|---|
| YAN ZHU,ET.AL.: "Preparation and applications of weak acid cation exchanger based on monodisperse poly(ethylvinylbenzene-co-divinylbezene) beads", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| 施青红 等: "弱酸型阳离子色谱填料的研制及性能评价", 《分析测试学报》 * |
| 杨春霞: "亲水单分散聚合物基质阳离子色谱柱的制备及其应用", 《分析化学》 * |
| 郭龑茹 等: "新型弱酸性阳离子色谱柱的制备及非抑制型离子色谱法电导检测", 《浙江大学学报（理学版）》 * |
| 陈永欣 等: "自制阳离子色谱柱测定有机胺", 《浙江大学学报（理学版）》 * |
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| CN108276526A (en) * | 2018-01-26 | 2018-07-13 | 北京石油化工学院 | A kind of high carrying capacity large aperture polymer cation displacement chromatography medium and its preparation |
| CN108276526B (en) * | 2018-01-26 | 2020-01-17 | 北京石油化工学院 | High-load large-aperture polymer cation exchange chromatography medium and preparation thereof |
| CN109705273A (en) * | 2019-01-11 | 2019-05-03 | 青岛普仁仪器有限公司 | A kind of preparation method of Subacidity cation chromatographic column filler |
| CN109705273B (en) * | 2019-01-11 | 2021-01-12 | 青岛普仁仪器有限公司 | Preparation method of weakly acidic cation chromatographic column packing |
| CN112588215A (en) * | 2020-11-24 | 2021-04-02 | 北方民族大学 | Coating type cellulose high-crosslinking polymer microsphere chiral stationary phase and preparation method and application thereof |
| CN112588215B (en) * | 2020-11-24 | 2023-01-31 | 北方民族大学 | Coating type cellulose high cross-linked polymer microsphere chiral stationary phase and preparation method and application thereof |
| CN116272921A (en) * | 2023-02-15 | 2023-06-23 | 青岛盛瀚色谱技术有限公司 | Monodisperse weakly acidic cation chromatographic packing and preparation method and application thereof |
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