CN102941074A - Preparation method of surface-grafting anion chromatography stationary phase - Google Patents
Preparation method of surface-grafting anion chromatography stationary phase Download PDFInfo
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Abstract
The invention relates to an anion chromatographic column a preparation method thereof, particularly relates to a preparation method of a surface-grafting anion chromatography stationary phase. The method disclosed herein is characterized by: preparing monodispersed linear polystyrene microspheres seeds by dispersion polymerization, activating the seeds, then synthesizing polystyrene-divinyl benzene-glycidyl methacrylate microballoons by one-step seed swelling method, and extracting to remove the pore forming agent; adopting multi-step grafting synthetic method, taking methylamine and 1,4-butanediol diglycidyl ether as raw materials, and introducing a large amount of positively charged quaternary ammonium groups as the anion exchange functional group to the surface of the prepared polystyrene-divinyl benzene-glycidyl methacrylate microballoons; and packing by homogenate method. According to the invention, the method disclosed herein has the advantages of low cost and simple process, the prepared filling material has uniform granularity and has no need to be screened, and the particle size distribution is narrow.
Description
Technical field
The present invention relates to a kind of anion chromatographic column and preparation method thereof, particularly relate to the fixedly preparation method of phase of surface-grafted type anion chromatographic.
Background technology
Chromatography of ions (being called for short IC) belongs to a kind of of high performance liquid chromatography, along with popularizing of chromatographic technique, just progressively be applied to every field, existing oneself is widely used at environmental monitoring, electric power and energy industry, food beverage industry, electron trade, life science, chemical industry and pharmaceutical industry etc.H.Small in 1975 and partner thereof have delivered first piece of chromatography of ions paper, and the same year, commercial apparatus came out.The ion chromatographic separation mode can be divided into high-effect ionic exchange chromatography, ion exclusion chromatography and ion pair chromatogram.Chromatography of ions has fast, sensitive, selectively good and measure simultaneously multi-component advantage, it is existing that oneself becomes a kind of the most effective instruments such as carbohydrate in yin, yang ion and partial organic substances and the biological sample, amino acid, peptide, protein of analyzing.Compare with the chromatogram analysis method of other type, the development speed of chromatography of ions is very fast and still have huge development space.
The chromatography of ions filler partly is comprised of insoluble matrix and fixing charged ion, and it selectively depends primarily on the character of chromatographic stationary phases.At present, mainly comprise mutually two kinds of inorganic matrix and polymer substrates at chromatography of ions field extensive use fixing.Silica matrix has excellent mechanical property and is easy to the characteristics of chemical modification, is widely used in fixedly phase system of chromatography of ions.But the deficiency of silica matrix filler maximum is its tolerance pH value be limited in scope (being generally 2-8); Polymer-based Chiral stationary phase comprises styrene-divinylbenzene and polymethacrylate polymer, often can tolerate widely pH value scope.Its major defect is rigidity and organic solvent-resistant aspect poor-performing, and then causes its limited resistance to pressure and Swelling.
The Ionized method of modifying of chromatography of ions filler mainly can be divided into four kinds: (1) carries out ionization by hydrophobic suction-operated with the surface that amphiprotic substance is coated in basic ball; (2) by chemical modification such as concentrated acid sulfonation effect, directly carry out ionization on the surface of basic ball; Then the compound that (3) will have larger molecular weight is modified large molecule by chemical reaction and resin-bonded; (4) be attached on the matrix microspheres with electrostatic force by the individual layer latex with the function base.Most widely used chromatograph packing material is the chromatograph packing material of latex agglomeration type now, surface agglomeration type anion chromatographic filling material has the separative efficiency height, the advantage that analysis speed is fast, yet it has complicated process of preparation simultaneously, the filler sphere diameter is inhomogeneous, the column capacity of anion chromatographic column is little, not the weakness such as acid and alkali-resistance.
Summary of the invention
The present invention is just for inorganic matrix filler acid and alkali-resistance not, poor chemical stability, produce easily non-specific not high with Irreversible Adsorption and organic substrate filler rigidity, pore structure is complicated, produce easily the shortcomings such as expansion and contraction, prior art is improved, a kind of method of novel surface-grafted type anion chromatographic Stationary phase preparation is provided.The advantages such as it is simple that the present invention has preparation technology, and the filler sphere diameter is even, and exchange capacity can be controlled, and resistance to acids and bases is strong.
The invention provides the preparation method of surface-grafted type chromatographic stationary phases, comprise the preparation of single seed-dispersed and the preparation of surface-grafted type chromatographic stationary phases, concrete technical scheme of the present invention is as follows:
Surface-grafted type anion chromatographic provided by the invention is the preparation method of phase fixedly, adopt dispersion copolymerization method to prepare monodispersed linear polystyrene microballoon seed, behind seed activation, adopt single step seed swelling method, synthetic polystyrene-divinylbenzene-GMA microballoon, pore-foaming agent is removed in extracting; Adopt multistep grafting synthetic method, with methylamine and 1, the 4-butanediol diglycidyl ether is raw material, introduces a large amount of positively charged quaternary ammonium groups as the anion exchange functional group at the polystyrene-divinylbenzene that makes-GMA microsphere surface; With homogenate method dress post, concrete preparation process is:
A. adopt dispersion copolymerization method to synthesize monodispersed linear polystyrene microballoon seed
Take styrene as monomer, polyvinylpyrrolidone is as stabilizing agent, and azodiisobutyronitrile is initator, in the mixed reaction media of second alcohol and water, generate monodispersed linear polystyrene microballoon seed by radical polymerization, seed particle size is between 1 ~ 3 μ m, and particle diameter is even, need not classification;
B. adopt single step seed swelling method synthetic polystyrene-divinylbenzene-GMA microballoon
Dibutyl phthalate mixed with synthetic single Decentralized Linear polystyrene microsphere make seed activation, rear adding monomer styrene stirs, the monomer GMA, the crosslinking agent divinylbenzene, emulsifier sodium lauryl sulfate, the stabilizing agent polyvinyl alcohol, initator benzoyl peroxide and pore-foaming agent toluene carry out swelling; Then add thermal booster reaction and make monomer polymerization, prepare monodispersed polystyrene-divinylbenzene-GMA microballoon; Polymer microballoon adopts deionized water, ethanol to clean, and needs after the oven dry through toluene extrct emulsion breaker, stabilizing agent etc.;
C. adopt the multistep synthetic method to modify polystyrene-divinylbenzene-GMA microballoon
Aminated reagent methylamine is fully mixed with the polystyrene-divinylbenzene that synthesizes-GMA microballoon, then add thermal booster reaction; Use subsequently the washed with de-ionized water microballoon, add the quaternizing agent BDDE, then add thermal booster reaction; Repeat above aminated and quaternised step, can change the organic number of plies of surface charging by regulating the number of times that repeats, thus the ion exchange capacity of control chromatograph packing material; Use washed with de-ionized water, homogenate method dress post.
The present invention is in monodispersed linear polystyrene microballoon seed is synthetic, reaction medium is ethanol water, concentration is 75 ~ 100%(v/v), the concentration of monomer styrene is 5 ~ 30%(m/m) of total amount, stabilizing agent polyvinylpyrrolidone consumption is 0.5 ~ 4%(m/v) of reaction medium, and initator azodiisobutyronitrile consumption is 1 ~ 5%(m/m) of monomer consumption, and reaction temperature is 40 ~ 85 ℃, mixing speed is at 100 ~ 400 rev/mins, and the reaction time is 8 ~ 24 hours.
The present invention is in the process of single step seed swelling method synthetic polystyrene-divinylbenzene-GMA microballoon, monomer styrene concentration is 10 ~ 20%(m/m) of total organic phase, monomer GMA concentration is 2 ~ 4%(m/m) of total organic phase, making the degree of cross linking excursion of complex microsphere by the consumption of regulating the crosslinking agent divinylbenzene is 10 ~ 75%(m/m), the emulsifier sodium lauryl sulfate consumption accounts for 2 ~ 4% (m/m) of total organic phase, stabilizing agent polyvinyl alcohol consumption is 0.5 ~ 5%(m/m) of total amount, initator benzoyl peroxide consumption is 0.4 ~ 1.5% (m/m) of monomer consumption, pore-foaming agent toluene consumption is 20 ~ 70% (m/m) of total organic phase, swelling ratio is 10 ~ 70 times, emulsifying temperature is 20 ~ 35 ℃, 60 ~ 85 ℃ of reaction temperatures, 100 ~ 300 rev/mins of mixing speeds, 12 ~ 48 hours reaction time, the particle diameter of synthetic polystyrene-divinylbenzene-GMA base ball distributes very narrow particle size range between 6-8 μ m, the basic ball that is synthesized is evenly high, need not to carry out classification and screening (as shown in Figure 1).
The granularity of basic ball of the present invention is to control by the selection of pore-foaming agent, crosslinking agent, dispersion stabilizer solubility, swelling temperature, reaction temperature, initiator concentration and swelling ratio.
The present invention modifies in the process of polystyrene-divinylbenzene-GMA microballoon in the multistep synthetic method, with methylamine and 1, the 4-butanediol diglycidyl ether is reaction raw materials, the concentration of aminated reagent methylamine is 4 ~ 10%(v/v), quaternizing agent 1, the concentration of 4-butanediol diglycidyl ether is 10 ~ 30%(v/v), alternately repeats aminated and quaternised step, and the microballoon after the modification as shown in Figure 2.Can change the organic number of plies of surface charging by regulating the number of times that repeats, thus the ion exchange capacity of control chromatograph packing material.
Surface-grafted type polymer chromatographic column provided by the invention is take polystyrene-divinylbenzene-GMA microballoon as matrix, at a large amount of quaternary ammonium group positive charges of microsphere surface chemistry covalent bonding as the anion exchange functional group.
Improve one's methods as a kind of, the surface-grafted type chromatographic column that the present invention prepares can be applied in the ion-exchange chromatography steadily in the long term, realizes preferably F
-, Cl
-, NO
2 -, Br
-, NO
3 -, SO
4 2-, PO
4 3-Separation etc. conventional inorganic anion; Compare with latex agglomeration type chromatograph packing material, each ion especially fluorine ion can well be separated with the water negative peak.
The present invention has following advantage:
Polystyrene-divinylbenzene provided by the invention-GMA method for preparing microsphere, cost is low, and technique is simple, and the filler epigranular of preparation need not screening, narrow diameter distribution.
Multistep synthetic method provided by the invention is carried out the quaternized modification of surface grafting, and the ion exchange capacity of chromatograph packing material can control on demand, for the preparation of the ion chromatographic column of different exchange capacities; The surface-grafted type chromatographic column for preparing can be applied to ion-exchange chromatography steadily in the long term, realizes preferably F
-, Cl
-, NO
2 -, Br
-, NO
3 -, SO
4 2-, PO
4 3-Separation; Compare with latex agglomeration type chromatograph packing material, each ion especially fluorine ion can well be separated with the water negative peak.
It is stable that surface-grafted type polymer chromatograph packing material provided by the invention has chromatographic performance, and ion selectivity is good, the separative efficiency high; Adopting polystyrene-divinylbenzene-GMA microballoon is matrix, and chemical stability is better, can tolerate broad pH value scope.
Description of drawings
Fig. 1 is that polystyrene-divinylbenzene-GMA filler microballoon amplifies 10000 times scanning electron microscope (SEM) photograph;
Fig. 2 is that surface-grafted type polystyrene-divinylbenzene-GMA benzene filler microballoon amplifies 10000 times scanning electron microscope (SEM) photograph;
Fig. 3 is the separate colors spectrogram of seven kinds of conventional anion;
Among Fig. 3,1-F
-(2ppm), 2-Cl
-(4ppm), 3-NO
2 -(10ppm), 4-Br
-(10ppm), 5-NO
3 -(10ppm), 6-SO
4 2-(10ppm), 7-PO
4 3-(10ppm).
The specific embodiment
Embodiment 1: the manufacturing process of surface-grafted type polystyrene-divinylbenzene-GMA filler is as follows, the steps include:
1, first by the single Decentralized Linear polystyrene seed of synthetic particle diameter 1 ~ 3 μ m of dispersion copolymerization method, reaction medium is ethanol water, concentration is 75 ~ 100%(v/v), the concentration of monomer styrene is 5 ~ 30%(m/m) of total amount, stabilizing agent polyvinylpyrrolidone consumption is 0.5 ~ 4%(m/v) of reaction medium, and initator azodiisobutyronitrile consumption is 1 ~ 5%(m/m) of monomer consumption, 40 ~ 85 ℃ of reaction temperatures, mixing speed is at 100 ~ 400 rev/mins, 8 ~ 24 hours reaction time;
2, be monodisperse polystyrene-divinylbenzene of 10 ~ 75%-GMA microballoon by the standby degree of cross linking that obtains of seed swelling legal system then.Monomer styrene concentration is 10 ~ 20%(m/m) of total organic phase, monomer GMA concentration is 2 ~ 4%(m/m) of total organic phase, making the degree of cross linking excursion of complex microsphere by the consumption of regulating the crosslinking agent divinylbenzene is 10 ~ 75%(m/m), the emulsifier sodium lauryl sulfate consumption accounts for 2 ~ 4% (m/m) of total organic phase, stabilizing agent polyvinyl alcohol consumption is 0.5 ~ 5%(m/m) of total amount, initator benzoyl peroxide consumption is 0.4 ~ 1.5% (m/m) of monomer consumption, pore-foaming agent toluene consumption is 20 ~ 70% (m/m) of total organic phase, swelling ratio is 10 ~ 70 times, emulsifying temperature is 20 ~ 35 ℃, 60 ~ 85 ℃ of reaction temperatures, 100 ~ 300 rev/mins of mixing speeds, 12 ~ 48 hours reaction time obtained uniform monodisperse polystyrene-divinylbenzene-GMA microsphere particle, and sphere diameter is 6 ~ 8 μ m, need not screening and classification, polymer microballoon is removed pore-foaming agent with the toluene extracting, water then, ethanol is cleaned;
3, with methylamine and 1, the 4-butanediol diglycidyl ether is reaction raw materials, adopt the multistep synthetic method to modify polystyrene-divinylbenzene-GMA microballoon, the concentration of aminated reagent methylamine is 4 ~ 10%(v/v), quaternizing agent 1, the concentration of 4-butanediol diglycidyl ether is 10 ~ 30%(v/v), and aminated and quaternised step comes again;
4, with the polystyrene-divinylbenzene of surface grafting-GMA filler water, ethanol is cleaned, and namely gets required filler, and the filler that makes is with homogenate method dress post;
5, adopt potassium hydroxide aqueous solution as mobile phase, flow velocity is 1 mL/min, adopts the inhibition electric conductivity detector that conventional anion is detected.
Embodiment 2: with reference to method and the step of embodiment 1
1, first by the synthetic particle diameter 1.8 μ m monodisperse polystyrene seed of dispersion copolymerization method, the concentration of monomer styrene is the 25%(m/m of total amount), stabilizing agent polyvinylpyrrolidone consumption is the 1.6%(m/v of reaction medium), initator azodiisobutyronitrile consumption is the 2.2%(m/m of monomer consumption), reaction medium is 90% ethanol water, 80 ℃ of reaction temperatures, mixing speed be at 300 rev/mins, 24 hours reaction time;
2, be monodisperse polystyrene-divinylbenzene of 50%-GMA microballoon by the standby degree of cross linking that obtains of seed swelling legal system then.Monomer styrene concentration is 14%(m/m), monomer GMA concentration is the 3%(m/m of total organic phase), the emulsifier sodium lauryl sulfate consumption is 2.5% (m/m), stabilizing agent polyvinyl alcohol consumption is 1.5%(m/m), initator benzoyl peroxide consumption is 0.8% (m/m), pore-foaming agent toluene consumption is 50% (m/m), swelling ratio is 55 times, emulsifying temperature is 20 ℃, 80 ℃ of reaction temperatures, 100 ~ 300 rev/mins of mixing speeds, 48 hours reaction time, polymer microballoon is removed pore-foaming agent with the toluene extracting, water then, ethanol is cleaned;
3, with methylamine and 1, the 4-butanediol diglycidyl ether is reaction raw materials, adopt the multistep synthetic method to modify polystyrene-divinylbenzene-GMA microballoon, the concentration of aminated reagent methylamine is 4 ~ 10%(v/v), quaternizing agent 1, the concentration of 4-butanediol diglycidyl ether is 10 ~ 30%(v/v), and aminated and quaternised step repeats two times;
4, with the polystyrene-divinylbenzene of surface grafting-GMA filler water, ethanol is cleaned, and namely gets required filler, and the filler that makes is with homogenate method dress post;
5, anion is measured result and 1(5 with embodiment 1 (5) method) consistent.
Embodiment 3:
1, first by the synthetic particle diameter 1.8 μ m monodisperse polystyrene seed of dispersion copolymerization method, the concentration of monomer styrene is the 25%(m/m of total amount), stabilizing agent polyvinylpyrrolidone consumption is the 1.6%(m/v of reaction medium), initator azodiisobutyronitrile consumption is the 2.2%(m/m of monomer consumption), reaction medium is 90% ethanol water, 80 ℃ of reaction temperatures, mixing speed be at 300 rev/mins, 24 hours reaction time;
2, then be monodisperse polystyrene-divinylbenzene of 50%-GMA microballoon by the standby degree of cross linking that obtains of seed swelling legal system, monomer styrene concentration is 14%(m/m), monomer GMA concentration is the 2%(m/m of total organic phase), the emulsifier sodium lauryl sulfate consumption is 2.5% (m/m), stabilizing agent polyvinyl alcohol consumption is 1.5%(m/m), initator benzoyl peroxide consumption is 0.8% (m/m), pore-foaming agent toluene consumption is 50% (m/m), swelling ratio is 55 times, emulsifying temperature is 20 ℃, 80 ℃ of reaction temperatures, 100 ~ 300 rev/mins of mixing speeds in 48 hours reaction time, are removed pore-foaming agent with polymer microballoon with the toluene extracting, then water, ethanol is cleaned;
3, with methylamine and 1, the 4-butanediol diglycidyl ether is reaction raw materials, adopt the multistep synthetic method to modify polystyrene-divinylbenzene-GMA microballoon, the concentration of aminated reagent methylamine is 4%(v/v), quaternizing agent 1, the concentration of 4-butanediol diglycidyl ether is 10%(v/v), aminated and quaternised step repeats three times;
4, with the polystyrene-divinylbenzene filler water of surface grafting, ethanol is cleaned, and namely gets required filler, and the filler that makes fills post with the homogenate method;
5, anion is measured result and 1(5 with embodiment 1 (5) method) consistent.
Embodiment 4: the column performance test
Instrument: Dionex ICS 2000 ion chromatographs, Dionex electric conductivity detector, Dionex ASRS-ULTRA(4mm) self-reproduction suppresser;
Sample: F
-, Cl
-, NO
2 -, Br
-, NO
3 -, SO
4 2-, PO
4 3-(it is pure to be analysis);
Leacheate: potassium hydroxide aqueous solution;
Splitter: homemade filler is loaded the stainless steel column in 4.6 * 150mm;
Flow velocity: 1 mL/min.
Referring to accompanying drawing 3, be the chromatogram of seven kinds of conventional anion, 1-F in the chromatogram
-(2ppm), 2-Cl
-(4ppm), 3-NO
2 -(10ppm), 4-Br
-(10ppm), 5-NO
3 -(10ppm), 6-SO
4 2-(10ppm), 7-PO
4 3-(10ppm).
Below in conjunction with Figure of description technical scheme of the present invention is described further:
Fig. 1 is the scanning electron microscope (SEM) photograph (amplifying 10000 times) of polystyrene-divinylbenzene-GMA microballoon, by the observation to scanning electron microscope (SEM) photograph, the particle diameter of synthetic polystyrene-divinylbenzene-GMA base ball distribute very narrow and particle size range between 6-8 μ m, the basic ball that is synthesized is evenly high, need not to carry out classification and screening.
Fig. 2 is the scanning electron microscope (SEM) photograph (amplifying 10000 times) of surface-grafted type polystyrene-divinylbenzene-GMA microballoon, by the observation to scanning electron microscope (SEM) photograph, polystyrene-divinylbenzene after the quaternized modification of multistep grafting-GMA base ball is not damaged, and keeps preferably integrality.
Fig. 3 is the chromatogram of seven kinds of conventional anion, with Dionex ICS 2000 ion chromatographs, joins Dionex electric conductivity detector and Dionex ASRS-ULTRA(4mm) self-reproduction suppresser, carry out Performance Detection to homemade ion chromatographic column.1-F in the chromatogram
-(2ppm), 2-Cl
-(4ppm), 3-NO
2 -(10ppm), 4-Br
-(10ppm), 5-NO
3 -(10ppm), 6-SO
4 2-(10ppm), 7-PO
4 3-(10ppm) can access baseline separation, especially fluorine ion can separate fully with the water negative peak, can satisfy the qualitative and quantitative testing requirement when analyzing.
Claims (6)
1. the fixing preparation method of phase of a surface-grafted type anion chromatographic, it is characterized in that: take polystyrene-divinylbenzene-GMA as matrix, adopt dispersion copolymerization method to prepare monodispersed linear polystyrene microballoon seed, behind seed activation, adopt single step seed swelling method, synthetic polystyrene-divinylbenzene-GMA microballoon, pore-foaming agent is removed in extracting; Adopt the multistep synthetic method, take methylamine and BDDE as raw material, introduce a large amount of positively charged quaternary ammonium groups as the anion exchange functional group at the polystyrene-divinylbenzene that makes-GMA microsphere surface; With homogenate method dress post, concrete preparation process is:
A. adopt dispersion copolymerization method to synthesize monodispersed linear polystyrene microballoon seed
Take styrene as monomer, polyvinylpyrrolidone is as stabilizing agent, and azodiisobutyronitrile is initator, in the mixed reaction media of second alcohol and water, generate monodispersed linear polystyrene microballoon seed by radical polymerization, seed particle size is between 1 ~ 3 μ m, and particle diameter is even, need not classification;
B. adopt single step seed swelling method synthetic polystyrene-divinylbenzene-GMA microballoon
Dibutyl phthalate mixed with synthetic single Decentralized Linear polystyrene microsphere make seed activation, rear adding monomer styrene stirs, the monomer GMA, the crosslinking agent divinylbenzene, emulsifier sodium lauryl sulfate, the stabilizing agent polyvinyl alcohol, initator benzoyl peroxide and pore-foaming agent toluene carry out swelling; Then add thermal booster reaction and make monomer polymerization, prepare monodispersed polystyrene-divinylbenzene-GMA microballoon; Polymer microballoon adopts deionized water, ethanol to clean, and needs after the oven dry through toluene extrct emulsion breaker, stabilizing agent;
C. adopt the multistep synthetic method to modify polystyrene-divinylbenzene-GMA microballoon
Aminated reagent methylamine is fully mixed with the polystyrene-divinylbenzene that synthesizes-GMA microballoon, then add thermal booster reaction; Use subsequently the washed with de-ionized water microballoon, add the quaternizing agent BDDE, then add thermal booster reaction; Repeat above aminated and quaternised step, can change the organic number of plies of surface charging by regulating the number of times that repeats, thus the ion exchange capacity of control chromatograph packing material; Use washed with de-ionized water, homogenate method dress post.
2. the preparation method of surface-grafted type anion chromatographic filling material according to claim 1, it is characterized in that: in the described step (a), the quality m of monomer styrene is 5 ~ 30% of gross mass m, the quality m of stabilizing agent polyvinylpyrrolidone is 0.5 ~ 4% of reaction medium volume v, the quality m of initator azodiisobutyronitrile is 1 ~ 5% of monomer mass m, reaction medium is ethanol water, volume v concentration is 75 ~ 100%, reaction temperature is 40 ~ 85 ℃, mixing speed is at 100 ~ 400 rev/mins, and the reaction time is 8 ~ 24 hours.
3. the preparation method of surface-grafted type anion chromatographic filling material according to claim 1, it is characterized in that: in the described step (b), monomer styrene quality m is 10 ~ 20% of total organic phase quality m, monomer GMA quality m is 2 ~ 4% of total organic phase quality m, making the degree of cross linking quality m change in concentration scope of complex microsphere by the consumption of regulating the crosslinking agent divinylbenzene is 10 ~ 75%, emulsifier sodium lauryl sulfate quality m accounts for 2 ~ 4% of total organic phase quality m, stabilizing agent polyvinyl alcohol quality m is 0.5 ~ 5% of gross mass m, initator benzoyl peroxide quality m is 0.4 ~ 1.5% of monomer mass m, pore-foaming agent toluene quality m is 20 ~ 70% of total organic phase quality m, swelling ratio is 10 ~ 70 times, emulsifying temperature is 20 ~ 35 ℃, 60 ~ 85 ℃ of reaction temperatures, 100 ~ 300 rev/mins of mixing speeds, 12 ~ 48 hours reaction time, the particle diameter of synthetic polystyrene-divinylbenzene-GMA base ball distributes very narrow particle size range between 6-8 μ m, the basic ball that is synthesized is evenly high, need not to carry out classification and screening.
4. the preparation method of surface-grafted type anion chromatographic filling material according to claim 3, it is characterized in that: the granularity of described basic ball is to control by the selection of pore-foaming agent or crosslinking agent or dispersion stabilizer solubility or swelling temperature or reaction temperature or initiator concentration or swelling ratio.
5. the preparation method of surface-grafted type anion chromatographic filling material according to claim 1, it is characterized in that: in the described step (c), with methylamine and 1, the 4-butanediol diglycidyl ether is reaction raw materials, the volume v concentration of aminated reagent methylamine is 4 ~ 10%, quaternizing agent 1, the volume v concentration of 4-butanediol diglycidyl ether is 10 ~ 30%, alternately repeat aminated and quaternised step, can change the organic number of plies of surface charging by regulating the number of times that repeats, thus the ion exchange capacity of control chromatograph packing material.
6. according to claim 1 and 2 or the preparation method of 3 or 4 or 5 described surface-grafted type anion chromatographic filling materials, it is characterized in that: preparation-obtained surface-grafted type chromatographic column can be applied to ion-exchange chromatography steadily in the long term, realizes preferably F
-, Cl
-, NO
2 -, Br
-, NO
3 -, SO
4 2-, PO
4 3-Separation, each ion especially fluorine ion can well be separated with the water negative peak.
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