CN104941611B - The preparation method of graft type high power capacity dendrimer chromatography of ions fixed phase stuffing - Google Patents
The preparation method of graft type high power capacity dendrimer chromatography of ions fixed phase stuffing Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of novel graft type high power capacity dendrimer chromatography of ions fixed phase stuffing, the preparation method of graft type high power capacity dendrimer chromatography of ions stationary phase is provided, preparation including integer for dendrimer, the preparation of polystyrene divinylbenzene GMA (PS DVB GMA) microballoon, dendrimer grafting, the quaternized modification of dendrimer and the preparation of high power capacity dendrimer graft type anion chromatographic filling material.This method makes full use of the substantial amounts of epoxide group of PS DVB GMA microsphere surfaces and integer for the substantial amounts of terminal amido of dendrimer, microsphere surface is modified, reaction is fast, cycle is short, method is easy, the filler exchange capacity synthesized is high, the ion chromatographic column separating degree of preparation is good, peak shape symmetry is high, the separation available for fluorine ion, organic acid, carbohydrate.
Description
Technical field
The present invention relates to a kind of preparation method of chromatography of ions, more particularly to the graft type of dendrimer material modification
Application in the preparation of Gh capacity ion chromatography filler.
Background technology
Since invention in 1975, development speed comes out at the top chromatography of ions always, and ion chromatography technology is also more next
More it is widely used in the foundation of various complicated analysis methods and the analysis of multi-component material.Even so, chromatography of ions side
Method still has very big deficiency in the analysis of Cucumber.
Fluorine ion is a kind of trace element of trophism in human body, and excessive fluorine ion can all cause for human body and environment
Sizable harm, therefore there is highly important meaning for environmental monitoring and health to accurately measuring for content of fluoride ion
Justice.But very big deficiency in the chromatography of ions is to the continuous mode of fluorine ion also be present；1) fluorine ion is in anion exchange
Retain weaker in post, usually be difficult to separate with water negative peak, very big deviation can be caused to the measure of content of fluoride ion[1]；2) in fluorine
During ion measurement, the acid of some weak reservations makes signal analysis very difficult often with fluorine ion co-elute[2].On the other hand, increase
Add the column capacity of anion chromatographic column, the selectivity for improving chromatography of ions is such issues that solve most simple effective method.
Carbohydrate is the main energy sources for the activity of sustaining life, but human body is limited to the intake of sugar therefore daily daily
The detection of sugar content in diet, it is most important for the intake of control sugar and raising quality of the life.The measure side of carbohydrate at present
Method is a lot, but various deficiencies all be present, and surveying sugar using the chromatography of ions still has the problem of being difficult to overcome.Common monose
Or disaccharides such as fructose, glucose or sucrose are acidulous material (pKa is about 12), occurred using anion-exchange chromatography separation
Monose and disaccharides separating degree are low, are difficult to the problem of separation, on the other hand, we need further to improve chromatography of ions column capacity and selection
Property.
Bibliography：
1. king ten thousand is virgin, chromatography of ions survey fluorine ion and influence and improvement of the water negative peak to it, Chemical Industry in Guangzhou, and 2012,40:
40-42
2. Wang Ying is abundant, Hu Duoduo, Wang Qingshan, influence of the organic acid to ion-chromatographic determination fluorine ion, chemical analysis meter
Amount, 2014,23:40-42
The content of the invention
The present invention is directed to the demand of Gh capacity ion chromatography post, and the preparation method of graft type chromatographic stationary phases is changed
Enter, there is provided a kind of preparation method of high power capacity dendrimer fixed phase stuffing.The present invention is to polystyrene-divinylbenzene
Method for preparing microsphere further optimizes, and a large amount of epoxies are accessed in microsphere surface by adding GMA monomer
Base, and the advantages of give full play to dendrimer a large amount of end groups, has that packing material size is uniform, resistance to acids and bases, prepare it is simple,
The advantages that synthesis cycle is short, and column capacity is high, and separating degree is high, and peak shape is symmetrical.
The present invention is achieved through the following technical solutions：
The invention discloses a kind of preparation method of graft type high power capacity dendrimer modified ion chromatographic stationary phases, adopt
With styrene-divinylbenzene-GMA matrix, monodispersed linear polyphenyl is prepared with dispersion copolymerization method
Ethene microballoon seed, the seed synthetic surface after activation is carried to the polyphenyl second of a large amount of epoxy radicals using single step seed swelling method
Alkene-divinylbenzene-GMA (PS-DVB-GMA) microballoon, extracting remove pore-foaming agent, connect by chemistry
Polyamidoamine Dendrimers are grafted to microsphere surface, quaternary ammonium are used as using BDO glycidol ether (BDDE) by branch method
Change reagent, terminal amino group is converted into quaternary ammonium group, Polyamidoamine Dendrimers are passed through by methyl acrylate and ethylenediamine
Micheal additions synthesize with amidation process.
As a further improvement, the synthesis of Polyamidoamine Dendrimers of the present invention is the temperature at 20-30 DEG C
The lower progress of degree.
As a further improvement, in single dispersing linear polystyrene seed preparation process of the present invention, monomer benzene
The mass fraction of ethene is 5-30% (g/g), as stabilizer and controls its quality to account for reaction cumulative volume using polyvinylpyrrolidone
0.5-4% (g/ml), the quality of initiator azodiisobutyronitrile is the 1-5% (g/g) of monomer mass, and reaction medium is volume
Ethanol of the fraction between 75-100%, reaction temperature are 50-80 DEG C, and mixing speed is controlled in 100-400r/min, reaction
Between be 8-24h.
As a further improvement, one-step swelling method synthetic polystyrene-divinylbenzene-methyl-prop of the present invention
During olefin(e) acid glycidol ester microsphere, the quality of monomer styrene accounts for the 10-20% (g/g) of total organic phase quality, compound
The degree of cross linking quality m change in concentration scope of microballoon is in 10-75% (g/ml) and dosage by adjusting cross-linker divinylbenzene
Control, the quality of emulsifying agent dodecyl sodium sulfate are the 2-4% (g/g) of organic phase gross mass, the matter of stabilizer polyvinyl alcohol
Amount accounts for the 0.5-5% (g/g) of gross mass, and the quality of initiator benzoyl peroxide is the 0.4-1.5% (g/g) of gross mass, is caused
The quality of hole agent toluene is the 20-70% (g/g) of total organic phase quality, and it is 20-35 DEG C to control emulsifying temperature, swelling ratio 30-
70 times, reaction temperature is 60-85 DEG C, and mixing speed turns for 100-300, reaction time 18-48h.
As a further improvement, the particle diameter of microballoon of the present invention can by crosslinking agent, stably dispersing agent concentration,
Swelling temperature, pore-foaming agent, reaction temperature, initiator concentration and the regulation of swelling regulate and control.
As a further improvement, one-step swelling method synthetic polystyrene-divinylbenzene-methyl-prop of the present invention
During olefin(e) acid glycidol ester microsphere, in addition to styrene monomer, a large amount of GMA conducts are additionally added
Another monomer, make the polymer microballoon surface of synthesis directly with a large amount of active epoxy radicals, Glycidyl methacrylate
The quality of glyceride monomers is the 6-9% of organic phase gross mass.
As a further improvement, Polyamidoamine Dendrimers of the present invention pass through it is substantial amounts of with base ball surface
Epoxy reaction is directly grafted, then makes polyamide-amide with the reaction of quaternizing agent BDO glycidol ether Hybrid Heating
Dendrimer terminal amino group becomes positively charged quaternized ammonium groups, wherein for the BDO glycidol ether reacted
Concentration be 10-30%.
The invention has the advantages that：
1. polystyrene-divinylbenzene-GMA (PS-DVB-GMA) provided by the invention is micro-
Ball preparation technology is simple, stability is good, uniform particle sizes, and a large amount of epoxy radicals in surface make it have higher chemism, be easy into
One step chemical modification.
2. the preparation method of graft type high power capacity dendrimer fixed phase stuffing provided by the invention, uses dendrimer
Stationary phase stromal surface is modified, giving full play to dendrimer surface has the advantage of a large amount of functional groups, is repaiied in simplification
The capacity of ion chromatographic column filler is improved while adoring step.
3. the preparation method of graft type high power capacity dendrimer fixed phase stuffing provided by the invention, passes through a large amount of methyl
The addition of glycidyl acrylate and the modification of dendrimer substantially increase the capacity of chromatographic stationary phases, can solve from
The problem of less material of strength retention (such as carbohydrate) is difficult to efficiently separate in sub- chromatography.
4. the preparation method of graft type high power capacity dendrimer fixed phase stuffing provided by the invention, with traditional graft type
Chromatography of ions stationary phase is compared, and substantially increases column capacity, is expected to solve general anion chromatographic water negative peak overlapping with fluorine ion
And organic acid and fluorine ion such as are difficult to separate at the FAQs.
5. the preparation method of graft type high power capacity dendrimer fixed phase stuffing provided by the invention, is not only held by post
The raising of amount improves the separating degree of chromatography of ions, produces more preferable separating effect, while can ensure that chromatography of ions has more
Add symmetrical peak shape.
Brief description of the drawings
Fig. 1 is fixed phase stuffing SEM figures after modification；
Fig. 2 is fixed phase stuffing infrared spectrogram after modification；
Fig. 3 is self-control high power capacity graft type ion chromatographic column to fluorine ion retention figure；
Fig. 4 is self-control high power capacity graft type ion chromatographic column to chlorion retention figure.
Embodiment
The invention discloses a kind of preparation method of high power capacity dendrimer graft type chromatography of ions stationary phase, including：
The preparation of dendrimer, the system of polystyrene-divinylbenzene-GMA (PS-DVB-GMA) microballoon
Standby, dendrimer is in the grafting of microsphere surface, the quaternized modification of dendrimer and quaternized dendrimer graft type
The preparation of chromatograph stationary-phase stuffing, concrete technical scheme of the invention are as follows：
With styrene-divinylbenzene-GMA (PS-DVB-GMA) for matrix, dispersin polymerization is used
Method prepares monodispersed linear polystyrene microballoon seed, using single step seed swelling method by the seed synthetic surface band after activation
There are polystyrene-divinylbenzene-GMA (PS-DVB-GMA) microballoon of a large amount of epoxy radicals, extrct
Remove pore-foaming agent.The Polyamidoamine Dendrimers of synthesis are grafted to microsphere surface again, and with BDO glycidol ether
(BDDE) quaternizing agent is used as, terminal amino group is converted into electrically charged quaternary ammonium group, is finally homogenized method dress post.Dendrimer
(PAMAM) preparation, using methyl acrylate and ethylenediamine as raw material, synthesized by Micheal additions with amidation process, it is tree-shaped
Macromolecular (PAMAM) synthesis temperature is 20-30 DEG C.
In single dispersing linear polystyrene seed preparation process, the mass fraction of monomer styrene is 5-30% (g/g),
Using base vinylpyrrolidone as stabilizer and control its quality account for reaction cumulative volume 0.5-4% (g/ml), initiator azo two
The quality of isobutyronitrile is the 1-5% (g/g) of monomer mass, and reaction medium is ethanol of the volume fraction between 75-100%, instead
It is 50-80 DEG C to answer temperature, and mixing speed is controlled in 100-400r/min, reaction time 8-24h.
During swelling method prepares polystyrene-divinylbenzene-GMA microballoon, monomer benzene
The quality of ethene accounts for the 10-20% (g/g) of total organic phase quality, and the degree of cross linking quality m change in concentration scopes of complex microsphere are in 10-
75% (g/ml) and the dosage control by adjusting cross-linker divinylbenzene, the quality of emulsifying agent dodecyl sodium sulfate is to have
The 2-4% (g/g) of machine phase gross mass, the quality of stabilizer polyvinyl alcohol account for the 0.5-5% of gross mass (g/g), initiator peroxide
The matter for changing benzoyl is the 0.4-1.5% (g/g) of gross mass, and the quality of pore-foaming agent toluene is the 20-70% of total organic phase quality
(g/g) it is 20-35 DEG C, to control emulsifying temperature, and swelling ratio is 30-70 times, and reaction temperature is 60-85 DEG C, mixing speed 100-
300 turns, reaction time 18-48h, the polystyrene divinylbenzene microballoon uniformity of synthesis is higher, without further classification
Or screening, the particle diameter of polystyrene-divinylbenzene-GMA (PS-DVB-GMA) microballoon can pass through
Crosslinking agent, stably dispersing agent concentration, swelling temperature, pore-foaming agent, reaction temperature, initiator concentration and the regulation of swelling are adjusted
Control.
During one-step swelling method synthetic polymer microballoon, in addition to styrene monomer, a large amount of methacrylic acids are additionally added
Ethylene oxidic ester (GMA) is used as another monomer, makes the polymer microballoon surface of synthesis directly with a large amount of active rings
Epoxide, the quality for adding GMA monomer is the 6-9% of organic phase gross mass, makes full use of the compound
Epoxide group be grafted more dendrimers in microsphere surface, double to improve the capacity of chromatography of ions stationary phase, further
Increase reserve capability of the chromatography of ions to ion, the chromatography of ions stationary phase of high power capacity is obtained, to F-With the strong reservation of carbohydrate
Carbohydrate and F can be realized-With efficiently separating for organic acid.Compared with common chromatography of ions stationary phase, graft type high power capacity tree
Strong reservation of the shape macroion chromatographic stationary phases to anion can realize that fluorine ion and water negative peak can also obtain preferably
Separation.
In the present invention, the grafting and chemical modification of dendrimer, dendrimer by with the substantial amounts of ring of base ball surface
Epoxide reaction is directly grafted, then makes dendrimer last with the reaction of quaternizing agent BDO glycidol ether Hybrid Heating
Amino End Group becomes positively charged quaternized ammonium groups, wherein the concentration of the BDO glycidol ether for reacting is 10-
30%.
Fig. 1 is fixed phase stuffing SEM figures after modification, by image it can be seen that the microspherulite diameter of the inventive method preparation is equal
It is even；
Fig. 2 is fixed phase stuffing infrared spectrogram after modification, 3500cm in figure-1Stayed for epoxy ring-opening at more sharp peak
Under hydroxyl peak, 1450-1650cm-1For the phenyl ring absworption peak in polymer substrate, 1695cm-1Locate for phenyl ring absworption peak slightly
Overlapping C=O absworption peaks, 1100-1300cm-1For C-N and C-O absworption peaks, in 3000-3500cm-1There is no obvious biabsorption peak
Illustrate there is no free amino in filler, i.e. all free aminos in dendrimer end have all been quaternized with quaternary ammonium salt
Form is present.
Technical scheme is further described below by specific embodiment：
Embodiment 1：The preparation process of graft type high power capacity dendrimer chromatography of ions fixed phase stuffing is as follows, its step
For：
1st, integer takes 2mL ethylenediamine to be dissolved in 25mL methanol, ice-water bath for dendrimer (PAMAM) preparation
25g methyl acrylate is slowly added under stirring, 28 DEG C are to slowly warm up to after being added dropwise, stirring reaction 24h obtains 0.5G's
PAMAM；Take 5g0.5GPAMAM to be dissolved in 25mL methanol, 15g ethylenediamine is slowly added dropwise under ice-water bath stirring, is added dropwise
It is warming up to 28 DEG C slowly afterwards, stirring reaction 24h obtains the dendrimer (1.0GPAMAM) in integer generation.
2nd, the preparation of polystyrene seed, 1~3 μm of monodisperse polystyrene kind of particle diameter is synthesized by emulsion dispersion polymerization
Son, the concentration of monomer styrene are 15% (m/m) of total amount, and stabilizer polyvinylpyrrolidone dosage is the 2% of reaction medium
(m/v), initiator azodiisobutyronitrile dosage is 1% (m/m) of monomer dosage, and reaction medium is absolute ethyl alcohol, reaction temperature
60 DEG C, mixing speed is at 200 revs/min, 24 hours reaction time；
3rd, the poly- polystyrene-divinylbenzene-GMA of single dispersing is prepared in swelling method
(PS-DVB-GMA) microballoon, the quality of monomer styrene account for the 15% of total organic phase quality, add monomer methacrylic acid and shrink
The quality of glyceride (GMA) is the 4.5% of organic phase gross mass, and the dosage by adjusting cross-linker divinylbenzene controls compound
The degree of cross linking quality m concentration of microballoon is 55%, the quality of emulsifying agent dodecyl sodium sulfate is the 2% of organic phase gross mass, surely
The quality for determining agent polyvinyl alcohol accounts for the 5% of gross mass, and the matter of initiator benzoyl peroxide is the 0.4% of gross mass, toluene
Quality is the 20% of total organic phase quality, and it is 35 DEG C to control emulsifying temperature, and swelling ratio is 30 times, and reaction temperature is 70 DEG C, stirring
Speed is 200 turns, and the reaction time is polystyrene-divinylbenzene-GMA synthesized by 24h
(PS-DVB-GMA) microballoon uniformity is higher, without further classification or screening.
4th, using polystyrene-divinylbenzene-GMA microballoon as matrix, microsphere surface is passed through
Epoxy radicals and integer reacted for the terminal amino group of dendrimer, dendrimer is grafted to microsphere surface, then with Isosorbide-5-Nitrae-
Butanediol glycidol ether Hybrid Heating, reacted with dendrimer terminal amino group, terminal amido is changed into quaternary ammonium group.It is quaternized
The concentration of reagent 1,4- butanediol glycidol ethers is 30%.
5th, it is high power capacity polystyrene-divinylbenzene-Glycidyl methacrylate of dendrimer surface grafting is sweet
Grease filler ethanol and water are cleaned and obtain required filler, and obtained filler fills post with homogenate method.
6th, it is mobile phase with 20mM NaOH, conventional anion is detected using Suppressor conductivity detection device.
Embodiment 2：With reference to the method and steps of embodiment 1
1st, integer takes 2mL ethylenediamine to be dissolved in 25mL methanol, ice-water bath for dendrimer (PAMAM) preparation
25g methyl acrylate is slowly added under stirring, 28 DEG C are to slowly warm up to after being added dropwise, stirring reaction 24h obtains 0.5G's
PAMAM；Take 5g0.5GPAMAM to be dissolved in 25mL methanol, 15g ethylenediamine is slowly added dropwise under ice-water bath stirring, is added dropwise
It is warming up to 28 DEG C slowly afterwards, stirring reaction 24h obtains the dendrimer (1.0GPAMAM) in integer generation.
2nd, the preparation of polystyrene seed, 1~3 μm of monodisperse polystyrene kind of particle diameter is synthesized by emulsion dispersion polymerization
Son, the concentration of monomer styrene are 15% (m/m) of total amount, and stabilizer polyvinylpyrrolidone dosage is the 2% of reaction medium
(m/v), initiator azodiisobutyronitrile dosage is 1% (m/m) of monomer dosage, and reaction medium is absolute ethyl alcohol, reaction temperature
60 DEG C, mixing speed is at 200 revs/min, 24 hours reaction time；
3rd, the poly- polystyrene-divinylbenzene-GMA of single dispersing is prepared in swelling method
(PS-DVB-GMA) microballoon, the quality of monomer styrene account for the 15% of total organic phase quality, add monomer methacrylic acid and shrink
The quality of glyceride (GMA) is the 6% of organic phase gross mass, and the dosage by adjusting cross-linker divinylbenzene controls compound micro-
The degree of cross linking quality m concentration of ball is 55%, the quality of emulsifying agent dodecyl sodium sulfate is the 2% of organic phase gross mass, stable
The quality of agent polyvinyl alcohol accounts for the 5% of gross mass, and the matter of initiator benzoyl peroxide is the 0.4% of gross mass, the matter of toluene
Measure as the 20% of total organic phase quality, it is 35 DEG C to control emulsifying temperature, and swelling ratio is 30 times, and reaction temperature is 70 DEG C, stirring speed
Spend for 200 turns, the reaction time is polystyrene-divinylbenzene-GMA (PS- synthesized by 24h
DVB-GMA) microballoon uniformity is higher, without further classification or screening.
4th, using polystyrene-divinylbenzene-GMA microballoon as matrix, microsphere surface is passed through
Epoxy radicals and integer reacted for the terminal amino group of dendrimer, dendrimer is grafted to microsphere surface, then with Isosorbide-5-Nitrae-
Butanediol glycidol ether Hybrid Heating, reacted with dendrimer terminal amino group, terminal amido is changed into quaternary ammonium group.It is quaternized
The concentration of reagent 1,4- butanediol glycidol ethers is 30%.
5th, it is high power capacity polystyrene-divinylbenzene-Glycidyl methacrylate of dendrimer surface grafting is sweet
Grease filler ethanol and water are cleaned and obtain required filler, and obtained filler fills post with homogenate method.
6th, it is mobile phase with 20mM NaOH, conventional anion is detected using Suppressor conductivity detection device.
Embodiment 3：
1st, integer takes 2mL ethylenediamine to be dissolved in 25mL methanol, ice-water bath for dendrimer (PAMAM) preparation
25g methyl acrylate is slowly added under stirring, 28 DEG C are to slowly warm up to after being added dropwise, stirring reaction 24h obtains 0.5G's
PAMAM；Take 5g0.5GPAMAM to be dissolved in 25mL methanol, 15g ethylenediamine is slowly added dropwise under ice-water bath stirring, is added dropwise
It is warming up to 28 DEG C slowly afterwards, stirring reaction 24h obtains the dendrimer (1.0GPAMAM) in integer generation.
2nd, the preparation of polystyrene seed, 1~3 μm of monodisperse polystyrene kind of particle diameter is synthesized by emulsion dispersion polymerization
Son, the concentration of monomer styrene are 15% (m/m) of total amount, and stabilizer polyvinylpyrrolidone dosage is the 2% of reaction medium
(m/v), initiator azodiisobutyronitrile dosage is 1% (m/m) of monomer dosage, and reaction medium is absolute ethyl alcohol, reaction temperature
60 DEG C, mixing speed is at 200 revs/min, 24 hours reaction time；
3rd, the poly- polystyrene-divinylbenzene-GMA of single dispersing is prepared in swelling method
(PS-DVB-GMA) microballoon, the quality of monomer styrene account for the 15% of total organic phase quality, add monomer methacrylic acid and shrink
The quality of glyceride (GMA) is the 7.5% of organic phase gross mass, and the dosage by adjusting cross-linker divinylbenzene controls compound
The degree of cross linking quality m concentration of microballoon is 55%, the quality of emulsifying agent dodecyl sodium sulfate is the 2% of organic phase gross mass, surely
The quality for determining agent polyvinyl alcohol accounts for the 5% of gross mass, and the matter of initiator benzoyl peroxide is the 0.4% of gross mass, toluene
Quality is the 20% of total organic phase quality, and it is 35 DEG C to control emulsifying temperature, and swelling ratio is 30 times, and reaction temperature is 70 DEG C, stirring
Speed is 200 turns, and the reaction time is polystyrene-divinylbenzene-GMA synthesized by 24h
(PS-DVB-GMA) microballoon uniformity is higher, without further classification or screening.
4th, using polystyrene-divinylbenzene-GMA microballoon as matrix, microsphere surface is passed through
Epoxy radicals and integer reacted for the terminal amino group of dendrimer, dendrimer is grafted to microsphere surface, then with Isosorbide-5-Nitrae-
Butanediol glycidol ether Hybrid Heating, reacted with dendrimer terminal amino group, terminal amido is changed into quaternary ammonium group.It is quaternized
The concentration of reagent 1,4- butanediol glycidol ethers is 30%.
5th, it is high power capacity polystyrene-divinylbenzene-Glycidyl methacrylate of dendrimer surface grafting is sweet
Grease filler ethanol and water are cleaned and obtain required filler, and obtained filler fills post with homogenate method.
6th, it is mobile phase with 20mM NaOH, conventional anion is detected using Suppressor conductivity detection device.
Embodiment 4：
1st, integer takes 2mL ethylenediamine to be dissolved in 25mL methanol, ice-water bath for dendrimer (PAMAM) preparation
25g methyl acrylate is slowly added under stirring, 28 DEG C are to slowly warm up to after being added dropwise, stirring reaction 24h obtains 0.5G's
PAMAM；Take 5g0.5GPAMAM to be dissolved in 25mL methanol, 15g ethylenediamine is slowly added dropwise under ice-water bath stirring, is added dropwise
It is warming up to 28 DEG C slowly afterwards, stirring reaction 24h obtains the dendrimer (1.0GPAMAM) in integer generation.
2nd, the preparation of polystyrene seed, 1~3 μm of monodisperse polystyrene kind of particle diameter is synthesized by emulsion dispersion polymerization
Son, the concentration of monomer styrene are 15% (m/m) of total amount, and stabilizer polyvinylpyrrolidone dosage is the 2% of reaction medium
(m/v), initiator azodiisobutyronitrile dosage is 1% (m/m) of monomer dosage, and reaction medium is absolute ethyl alcohol, reaction temperature
60 DEG C, mixing speed is at 200 revs/min, 24 hours reaction time；
3rd, the poly- polystyrene-divinylbenzene-GMA of single dispersing is prepared in swelling method
(PS-DVB-GMA) microballoon, the quality of monomer styrene account for the 15% of total organic phase quality, add monomer methacrylic acid and shrink
The quality of glyceride (GMA) is the 9% of organic phase gross mass, and the dosage by adjusting cross-linker divinylbenzene controls compound micro-
The degree of cross linking quality m concentration of ball is 55%, the quality of emulsifying agent dodecyl sodium sulfate is the 2% of organic phase gross mass, stable
The quality of agent polyvinyl alcohol accounts for the 5% of gross mass, and the matter of initiator benzoyl peroxide is the 0.4% of gross mass, the matter of toluene
Measure as the 20% of total organic phase quality, it is 35 DEG C to control emulsifying temperature, and swelling ratio is 30 times, and reaction temperature is 70 DEG C, stirring speed
Spend for 200 turns, the reaction time is polystyrene-divinylbenzene-GMA (PS- synthesized by 24h
DVB-GMA) microballoon uniformity is higher, without further classification or screening.
4th, using polystyrene-divinylbenzene-GMA microballoon as matrix, microsphere surface is passed through
Epoxy radicals and integer reacted for the terminal amino group of dendrimer, dendrimer is grafted to microsphere surface, then with Isosorbide-5-Nitrae-
Butanediol glycidol ether Hybrid Heating, reacted with dendrimer terminal amino group, terminal amido is changed into quaternary ammonium group.It is quaternized
The concentration of reagent 1,4- butanediol glycidol ethers is 30%.
5th, it is high power capacity polystyrene-divinylbenzene-Glycidyl methacrylate of dendrimer surface grafting is sweet
Grease filler ethanol and water are cleaned and obtain required filler, and obtained filler fills post with homogenate method.
6th, it is mobile phase with 20mM NaOH, conventional anion is detected using Suppressor conductivity detection device.
Embodiment 5：Column performance is tested
Instrument：Vast CIC-100 chromatographs, the suppressors of SHY-A- III are contained, vast conductance pool detector is contained in Qingdao
Sample：F-(analysis is pure)
Leacheate：10mM NaOH solutions
Splitter：Self-made fill post
Flow velocity：1mL/min
Embodiment 6：Column performance is tested
Instrument：Vast CIC-100 chromatographs, the suppressors of SHY-A- III are contained, vast conductance pool detector is contained in Qingdao
Sample：Cl-(analysis is pure)
Leacheate：20mM NaOH solutions
Splitter：Self-made fill post
Flow velocity：1mL/min
Fig. 3 is to make high power capacity graft type ion chromatographic column by oneself to fluorine ion retention figure, to contain vast CIC-100 chromatographs
Contain vast conductance pool detector and the suppressors of SHY-A- III with Qingdao, using 10mM NaOH solutions as mobile phase, to it is homemade from
Sub- chromatographic column detects to the strength retention of fluorine ion, 1-F in chromatogram-(3ppm) retention time is 5.6min, with routine
Anion chromatographic column is compared, self-control high power capacity graft type ion chromatographic column it is more long to the retention time of fluorine ion, and with system peak
The separating effect of (water negative peak) is more preferable.
Fig. 4 is to make high power capacity graft type ion chromatographic column by oneself to chlorion retention figure, to contain vast CIC-100 chromatographs
Contain vast conductance pool detector and the suppressors of SHY-A- III with Qingdao, using 20mM NaOH solutions as mobile phase, to it is homemade from
Sub- chromatographic column detects to the strength retention of chlorion, 1-Cl in chromatogram-(5ppm) retention time is 35.8min, much
Retention time in being detected more than conventional anion, illustrate that there is the homemade chromatography of ions stationary phase of the present invention higher post to hold
Amount.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair
It is bright.The invention is not restricted to embodiment here, those skilled in the art change according to the announcement of the present invention for what the present invention made
Entering and change all should be within protection scope of the present invention.
Claims (5)
1. a kind of graft type high power capacity dendrimer modified ion chromatographic stationary phases preparation method, it is characterised in that using benzene
Ethene-divinylbenzene-GMA matrix, monodispersed linear polystyrene is prepared with dispersion copolymerization method
Microballoon seed, the seed synthetic surface after activation is carried to the polystyrene-two of a large amount of epoxy radicals using single step seed swelling method
Vinyl benzene-GMA (PS-DVB-GMA) microballoon, extracting removes pore-foaming agent, by chemical graft process,
Polyamidoamine Dendrimers are grafted to microsphere surface, quaternized examination is used as using BDO glycidol ether (BDDE)
Agent, terminal amino group is converted into quaternary ammonium group, described Polyamidoamine Dendrimers are passed through by methyl acrylate and ethylenediamine
Micheal additions synthesize with amidation process.
2. graft type high power capacity dendrimer modified ion chromatographic stationary phases preparation method according to claim 1, its
It is characterised by, the synthesis of described Polyamidoamine Dendrimers is carried out at a temperature of 20-30 DEG C.
3. graft type high power capacity dendrimer modified ion chromatographic stationary phases preparation method according to claim 1, its
It is characterised by, in described single dispersing linear polystyrene seed preparation process, the mass fraction of monomer styrene is 5-30%
(g/g), using polyvinylpyrrolidone as stabilizer and control its quality account for reaction cumulative volume 0.5-4% (g/ml), initiator
The quality of azodiisobutyronitrile is the 1-5% (g/g) of monomer mass, and reaction medium is second of the volume fraction between 75-100%
Alcohol, reaction temperature are 50-80 DEG C, and mixing speed is controlled in 100-400r/min, reaction time 8-24h.
4. graft type high power capacity dendrimer modified ion chromatographic stationary phases preparation method according to claim 1, its
It is characterised by the process of single step seed swelling method synthetic polystyrene-divinylbenzene-GMA microballoon
In, in addition to styrene monomer, a large amount of GMAs are additionally added as another monomer, make the polymer of synthesis
Microsphere surface is directly total for organic phase with a large amount of active epoxy radicals, the quality of GMA monomer
The 6-9% of quality.
5. graft type high power capacity dendrimer modified ion chromatographic stationary phases preparation method according to claim 1, its
Described Polyamidoamine Dendrimers are characterised by by being directly grafted with the substantial amounts of epoxy reaction of base ball surface, then with
The reaction of quaternizing agent 1,4- butanediol glycidol ethers Hybrid Heating makes Polyamidoamine Dendrimers terminal amino group become band
The quaternized ammonium groups of positive charge, wherein the concentration of the BDO glycidol ether for reacting is 10-30%.
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| CN105396628B (en) * | 2015-12-06 | 2018-02-23 | 杭州飞山浩科技有限公司 | The preparation method of polyethylene polyamine graft modification polystyrene divinylbenzene chromatography of ions filler |
| CN105664886A (en) * | 2016-01-14 | 2016-06-15 | 杭州飞山浩科技有限公司 | Preparation method of weak acid cation exchange stationary phase |
| CN105597716A (en) * | 2016-01-14 | 2016-05-25 | 杭州飞山浩科技有限公司 | Preparation method of anion exchange chromatography stationary phase |
| CN107262064A (en) * | 2017-07-26 | 2017-10-20 | 浙江大学 | A kind of preparation method of daiamid grafted graphene oxide cladded type biological micromolecule adsorbent |
| CN110452319B (en) * | 2018-05-07 | 2020-05-05 | 中国科学院大连化学物理研究所 | Preparation method and application of dendrimer functional polymer |
| CN109608585B (en) * | 2018-12-20 | 2021-06-15 | 华东理工大学 | Surface graft polymerization type anion chromatographic stationary phase, preparation method thereof and ion chromatographic column |
| CN111659356B (en) * | 2019-03-06 | 2021-09-24 | 中国科学院大连化学物理研究所 | Preparation and application of polyethyleneimine modified reversed phase/strong anion exchange mixed mode polymer |
| CN113019349A (en) * | 2021-03-02 | 2021-06-25 | 河北欧润科学仪器股份有限公司 | Preparation method of anion chromatographic stationary phase |
| CN114213581A (en) * | 2021-12-20 | 2022-03-22 | 南京亘闪生物科技有限公司 | Preparation method of hydrophilic polyacrylate crosslinked microspheres |
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| CN101081338A (en) * | 2006-05-29 | 2007-12-05 | 北京化工大学 | Method for preparation of novel capillary column electric chromatographic column using dendritic macromole polyamide-amine as linking fixed phase |
| CN102941074A (en) * | 2012-10-31 | 2013-02-27 | 浙江大学 | Preparation method of surface-grafting anion chromatography stationary phase |
| CN104130422A (en) * | 2014-07-25 | 2014-11-05 | 鲁东大学 | Preparation method of silica gel-bonded polyamidoamine (PAMAM) dendrimer adsorbent |
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| CN101081338A (en) * | 2006-05-29 | 2007-12-05 | 北京化工大学 | Method for preparation of novel capillary column electric chromatographic column using dendritic macromole polyamide-amine as linking fixed phase |
| CN102941074A (en) * | 2012-10-31 | 2013-02-27 | 浙江大学 | Preparation method of surface-grafting anion chromatography stationary phase |
| CN104130422A (en) * | 2014-07-25 | 2014-11-05 | 鲁东大学 | Preparation method of silica gel-bonded polyamidoamine (PAMAM) dendrimer adsorbent |
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