CN104941611A - Preparation method of novel grafting high-capacity dendrimer ion chromatography stationary phase stuffing - Google Patents
Preparation method of novel grafting high-capacity dendrimer ion chromatography stationary phase stuffing Download PDFInfo
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Abstract
The invention relates to a preparation method of a novel grafting high-capacity dendrimer ion chromatography stationary phase stuffing. The preparation method of the grafting high-capacity dendrimer ion chromatography stationary phase stuffing comprises preparation of integer dendrimers, preparation of polystyrene-divinyl benzene-glycidyl methacrylate (PS-DVB-GMA) microspheres, grafting and quaternization modification of dendrimer and preparation of a high-capacity dendrimer grafting anion chromatography stationary phase stuffing. According to the method, lots of epoxy groups on the surface of PS-DVB-GMA microspheres and lots of terminal amino groups of integer dendrimers are fully utilized to modify the surface of microspheres. The reaction is fast, period is short, the method is simple and convenient, and the synthesized stuffing has high exchange capacity. A prepared ion chromatographic column has good resolution and high peak shape symmetry and can be used in separation of fluorinion, organic acid and saccharides.
Description
Technical field
The present invention relates to a kind of preparation method of chromatography of ions, particularly relate to the application in the graft type Gh capacity ion chromatography filler preparation of dendrimer material modification.
Background technology
Chromatography of ions is since invention in 1975, and development speed comes out at the top always, and ion chromatography technology is also more and more widely used in the various foundation of complex analyses method and the analysis of multi-component material.Even so, still there is very large deficiency in ion chromatographic method in the analysis of Cucumber.
Fluorine ion is the trace element of a kind of trophism in human body, and excessive fluorine ion all can cause sizable harm for human body and environment, is therefore of great significance for environmental monitoring and health tool accurately measuring of content of fluoride ion.But, in the mensuration process of the chromatography of ions to fluorine ion, also there is very large deficiency; 1) fluorine ion retains more weak in anion-exchange column, is usually difficult to be separated with water negative peak, can cause very large deviation to the mensuration of content of fluoride ion
[1]; 2) in Fluorine Ion Determination process, the acid of some weak reservations often and fluorine ion co-elute, makes signal analysis very difficult
[2].To this, increase the column capacity of anion chromatographic column, improve chromatography of ions selective be solve the most simple effective method of this kind of problem.
Carbohydrate is the main energy sources of the activity of sustaining life, but the human body intake of every day to sugar is limited, the therefore detection of sugar content in diet, takes in and to improve quality of the life most important for control sugar.The assay method of current carbohydrate is a lot, but all there is various deficiency, adopts the chromatography of ions to survey sugar and still there is the problem being difficult to overcome.Common monose or disaccharides such as fructose, glucose or sucrose are acidulous material (pKa is about 12), adopt anion-exchange chromatography to be separated to there will be monose low with disaccharides separating degree, be difficult to the problem that is separated, to this, we need to improve further chromatography of ions column capacity and selective.
Bibliography:
1. king ten thousand is virgin, and chromatography of ions surveys fluorine ion and water negative peak to its impact and improvement, Chemical Industry in Guangzhou, 2012,40:40-42
2. Wang Ying is abundant, Hu Duoduo, Wang Qingshan, and organic acid is on the impact of ion-chromatographic determination fluorine ion, and chemical analysis measures, 2014,23:40-42
Summary of the invention
The present invention is directed to the demand of Gh capacity ion chromatography post, the preparation method of graft type chromatographic stationary phases is improved, provide a kind of preparation method of novel high power capacity dendrimer fixed phase stuffing.P-poly-phenyl ethene-divinylbenzene microspheres preparation method of the present invention optimizes further, a large amount of epoxy radicals is accessed at microsphere surface by adding GMA monomer, and give full play to the advantage of a large amount of end group of dendrimer, have packing material size even, resistance to acids and bases, preparation is simple, synthesis cycle is short, the advantages such as 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 novel graft type high power capacity dendrimer modified ion chromatographic stationary phases, adopt styrene-divinylbenzene-GMA matrix, monodispersed linear polystyrene microballoon seed is prepared with dispersion copolymerization method, adopt single step seed swelling method by polystyrene-divinylbenzene-GMA (PS-DVB-GMA) microballoon of the seed synthetic surface after activation with a large amount of epoxy radicals, extracting removing pore-foaming agent, pass through chemical graft process, Polyamidoamine Dendrimers is grafted to microsphere surface, with 1, 4-butanediol glycidol ether (BDDE) is as quaternizing agent, terminal amino group is converted into quaternary ammonium group.
As improving further, Polyamidoamine Dendrimers of the present invention is synthesized by Micheal addition and amidation process by methyl acrylate and ethylenediamine.
As improving further, the synthesis of Polyamidoamine Dendrimers-amine of the present invention carries out at the temperature of 20-30 DEG C.
As improving further, in single dispersing linear polystyrene Spawn preparation process of the present invention, the mass fraction of monomer styrene is 5-30% (g/g), be stabilizing agent with polyvinylpyrrolidone and control the 0.5-4% (g/ml) that its quality accounts for reaction cumulative volume, the quality of initator azodiisobutyronitrile is the 1-5% (g/g) of monomer mass, reaction medium is the ethanol of volume fraction between 75-100%, reaction temperature is 50-80 DEG C, mixing speed controls at 100-400r/min, and the reaction time is 8-24h.
As improving further, in the process of one-step swelling method synthetic polystyrene-divinylbenzene-GMA microballoon of the present invention, the quality of monomer styrene accounts for the 10-20% (g/g) of total organic phase quality, the degree of cross linking quality m change in concentration scope of complex microsphere is at 10-75% (g/ml) and by regulating the consumption of cross-linker divinylbenzene to control, the quality of emulsifying agent dodecyl sodium sulfate is the 2-4% (g/g) of organic phase gross mass, the quality of stabilizing agent polyvinyl alcohol accounts for the 0.5-5% (g/g) of gross mass, the quality of initator benzoyl peroxide is the 0.4-1.5% (g/g) of gross mass, the quality of pore-foaming agent toluene is the 20-70% (g/g) of total organic phase quality, control emulsifying temperature is 20-35 DEG C, swelling ratio is 30-70 times, reaction temperature is 60-85 DEG C, mixing speed is that 100-300 turns, reaction time is 18-48h.
As improving further, the particle diameter of microballoon of the present invention can by regulating and controlling crosslinking agent, stably dispersing agent concentration, swelling temperature, pore-foaming agent, reaction temperature, initiator concentration and swelling adjustment.
As improving further, in the process of one-step swelling method synthetic polystyrene-divinylbenzene-GMA microballoon of the present invention, except styrene monomer, also add a large amount of GMA as another kind of monomer, make the polymer microballoon of synthesis surface directly with the activated epoxy radicals of a large amount of tool, the quality of GMA monomer is the 6-9% of organic phase gross mass.
As improving further, Polyamidoamine Dendrimers of the present invention is by the epoxy reaction direct grafting a large amount of with base ball surface, again with quaternizing agent 1,4-butanediol glycidol ether Hybrid Heating reacts the quaternized ammonium groups making Polyamidoamine Dendrimers terminal amino group become positively charged, concentration wherein for the BDO glycidol ether reacted is 10-30%.
Tool of the present invention has the following advantages:
1. polystyrene-divinylbenzene-GMA (PS-DVB-GMA) microspheres provided by the invention simple, good stability, uniform particle sizes, the a large amount of epoxy radicals in surface makes it have higher chemism, is convenient to further chemical modification.
2. the preparation method of graft type high power capacity dendrimer fixed phase stuffing provided by the invention, with dendrimer, Stationary liquid stromal surface is modified, give full play to the advantage that dendrimer surface has a large amount of functional group, while simplifying modification step, improve the capacity of ion chromatographic column filler.
3. the preparation method of graft type high power capacity dendrimer fixed phase stuffing provided by the invention, add by a large amount of GMA the capacity substantially increasing chromatographic stationary phases with the modification of dendrimer, the problem that material (as carbohydrate) that in ion chromatography, strength retention is less is difficult to effectively be separated can be solved.
4. the preparation method of graft type high power capacity dendrimer fixed phase stuffing provided by the invention, compared with traditional graft type chromatography of ions Stationary liquid, substantially increase column capacity, be expected to solve general anion chromatographic water negative peak and be difficult to fluorine ion FAQs such as being separated with fluorine ion overlap and organic acid.
5. the preparation method of graft type high power capacity dendrimer fixed phase stuffing provided by the invention, does not improve the separating degree of chromatography of ions, produces better separating effect by means of only the raising of column capacity, can ensure that chromatography of ions has more symmetrical peak shape simultaneously.
Accompanying drawing explanation
Fig. 1 is that after modifying, fixed phase stuffing SEM schemes;
Fig. 2 is fixed phase stuffing infrared spectrogram after modifying;
Fig. 3 is that self-control novel high-capacity graft type ion chromatographic column is to fluorine ion retention figure;
Fig. 4 is that novel high-capacity graft type ion chromatographic column processed is to chlorion retention figure.
Detailed description of the invention
The invention discloses a kind of preparation method of novel high-capacity dendrimer graft type chromatography of ions Stationary liquid, comprise: the preparation of dendrimer, the preparation of polystyrene-divinylbenzene-GMA (PS-DVB-GMA) microballoon, dendrimer is in the preparation of the grafting of microsphere surface, the quaternized modification of dendrimer and quaternized dendrimer graft type chromatograph stationary-phase stuffing, and concrete technical scheme of the present invention is as follows:
With styrene-divinylbenzene-GMA (PS-DVB-GMA) for matrix, monodispersed linear polystyrene microballoon seed is prepared with dispersion copolymerization method, adopt single step seed swelling method by polystyrene-divinylbenzene-GMA (PS-DVB-GMA) microballoon of the seed synthetic surface after activation with a large amount of epoxy radicals, extracting removing pore-foaming agent.Again the Polyamidoamine Dendrimers of synthesis is grafted to microsphere surface, and using BDO glycidol ether (BDDE) as quaternizing agent, terminal amino group is converted into charged quaternary ammonium group, last homogenate method dress post.The preparation of dendrimer (PAMAM), with methyl acrylate and ethylenediamine for raw material, synthesized by Micheal addition and amidation process, dendrimer (PAMAM) synthesis temperature is 20-30 DEG C.
In single dispersing linear polystyrene Spawn preparation process, the mass fraction of monomer styrene is 5-30% (g/g), with base vinylpyrrolidone for stabilizing agent and control its quality account for reaction cumulative volume 0.5-4% (g/ml), the quality of initator azodiisobutyronitrile is the 1-5% (g/g) of monomer mass, reaction medium is the ethanol of volume fraction between 75-100%, reaction temperature is 50-80 DEG C, mixing speed controls at 100-400r/min, and the reaction time is 8-24h.
Prepare in polystyrene-divinylbenzene-GMA microballoon process at swelling method, the quality of monomer styrene accounts for the 10-20% (g/g) of total organic phase quality, the degree of cross linking quality m change in concentration scope of complex microsphere is at 10-75% (g/ml) and by regulating the consumption of cross-linker divinylbenzene to control, the quality of emulsifying agent dodecyl sodium sulfate is the 2-4% (g/g) of organic phase gross mass, the quality of stabilizing agent polyvinyl alcohol accounts for the 0.5-5% (g/g) of gross mass, the matter of initator benzoyl peroxide is the 0.4-1.5% (g/g) of gross mass, the quality of pore-foaming agent toluene is the 20-70% (g/g) of total organic phase quality, control emulsifying temperature is 20-35 DEG C, swelling ratio is 30-70 times, reaction temperature is 60-85 DEG C, mixing speed is that 100-300 turns, reaction time is 18-48h, the polystyrene divinylbenzene microballoon uniformity of synthesis is higher, without the need to 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 swelling adjustment regulate and control.
In one-step swelling method synthetic polymer microballoon process, except styrene monomer, also add a large amount of GMA (GMA) as another kind of monomer, make the polymer microballoon of synthesis surface directly with the activated epoxy radicals of a large amount of tool, the quality adding GMA monomer is the 6-9% of organic phase gross mass, make full use of the epoxide group of this compound at the more dendrimers of microsphere surface grafting, double the capacity that improve chromatography of ions Stationary liquid, further increase chromatography of ions is to the reserve capability of ion, obtain the chromatography of ions Stationary liquid of high power capacity, to F
-carbohydrate and F can be realized with the strong reservation of carbohydrate
-effectively be separated with organic acid.Compared with common chromatography of ions Stationary liquid, the strong reservation that novel graft type high power capacity dendrimer chromatography of ions fixes counter-anions can realize fluorine ion and also can be separated preferably with water negative peak.
In the present invention, the grafting of dendrimer and chemical modification, dendrimer is by the epoxy reaction direct grafting a large amount of with base ball surface, again with quaternizing agent 1,4-butanediol glycidol ether Hybrid Heating reacts the quaternized ammonium groups making dendrimer terminal amino group become positively charged, concentration wherein for the BDO glycidol ether reacted is 10-30%.
Fig. 1 is that after modifying, fixed phase stuffing SEM schemes, and can find out that microspherulite diameter prepared by the inventive method is even by image;
Fig. 2 is fixed phase stuffing infrared spectrogram after modifying, 3500cm in figure
-1comparatively sharp-pointed peak is the hydroxyl peak that epoxy ring-opening stays, 1450-1650cm
-1for the phenyl ring absworption peak in polymer substrate, 1695cm
-1place is C=O absworption peak slightly overlapping with phenyl ring absworption peak, 1100-1300cm
-1for C-N and C-O absworption peak, at 3000-3500cm
-1do not have obvious biabsorption peak to illustrate in filler do not have free amino, the free amino that namely dendrimer end is all is all quaternized to be existed with the form of quaternary ammonium salt.
Below by specific embodiment, technical scheme of the present invention is further described:
Embodiment 1: the preparation process of novel graft type high power capacity dendrimer chromatography of ions fixed phase stuffing is as follows, the steps include:
1, integer is for the preparation of dendrimer (PAMAM), the ethylenediamine getting 2mL is dissolved in the methyl alcohol of 25mL, ice-water bath slowly adds the methyl acrylate of 25g under stirring, and dropwises slowly to be warming up to 28 DEG C afterwards, and stirring reaction 24h obtains the PAMAM of 0.5G; Getting 5g0.5GPAMAM is dissolved in 25mL methyl alcohol, and ice-water bath stirs the lower ethylenediamine slowly dripping 15g, dropwises to be warming up to 28 DEG C slowly afterwards, and stirring reaction 24h obtains the dendrimer (1.0GPAMAM) in integer generation.
2, the preparation of polystyrene seed, by emulsion dispersion polymerization synthesis particle diameter 1 ~ 3 μm of monodisperse polystyrene seed, the concentration of monomer styrene is 15% (m/m) of total amount, stabilizing agent polyvinylpyrrolidone consumption is 2% (m/v) of reaction medium, initator azodiisobutyronitrile consumption is 1% (m/m) of monomer consumption, and reaction medium is absolute ethyl alcohol, reaction temperature 60 DEG C, mixing speed at 200 revs/min, 24 hours reaction time;
3, swelling method prepares single dispersing and gathers polystyrene-divinylbenzene-GMA (PS-DVB-GMA) microballoon, the quality of monomer styrene accounts for 15% of total organic phase quality, the quality adding monomer methacrylic acid ethylene oxidic ester (GMA) is 4.5% of organic phase gross mass, the degree of cross linking quality m concentration being controlled complex microsphere by the consumption of adjustment cross-linker divinylbenzene is 55%, , the quality of emulsifying agent dodecyl sodium sulfate is 2% of organic phase gross mass, the quality of stabilizing agent polyvinyl alcohol accounts for 5% of gross mass, the matter of initator benzoyl peroxide is 0.4% of gross mass, the quality of toluene is 20% of total organic phase quality, controlling emulsifying temperature is 35 DEG C, swelling ratio is 30 times, reaction temperature is 70 DEG C, mixing speed is 200 turns, the reaction time polystyrene synthesized by 24h-divinylbenzene-GMA (PS-DVB-GMA) microballoon uniformity is higher, without the need to further classification or screening.
4, with polystyrene-divinylbenzene-GMA microballoon for matrix, reacted by the epoxy radicals of microsphere surface and the integer terminal amino group for dendrimer, dendrimer is grafted to microsphere surface, again with 1,4-butanediol glycidol ether Hybrid Heating, react with dendrimer terminal amino group, make terminal amido become quaternary ammonium group.The concentration of quaternizing agent BDO glycidol ether is 30%.
5, the high power capacity of dendrimer surface grafting polystyrene-divinylbenzene-GMA filler ethanol and water are cleaned namely obtain required filler, obtained filler homogenate method dress post.
6, be mobile phase with the NaOH of 20mM, adopt Suppressor conductivity detection device to detect conventional anion.
Embodiment 2: with reference to method and the step of embodiment 1
1, integer is for the preparation of dendrimer (PAMAM), the ethylenediamine getting 2mL is dissolved in the methyl alcohol of 25mL, ice-water bath slowly adds the methyl acrylate of 25g under stirring, and dropwises slowly to be warming up to 28 DEG C afterwards, and stirring reaction 24h obtains the PAMAM of 0.5G; Getting 5g0.5GPAMAM is dissolved in 25mL methyl alcohol, and ice-water bath stirs the lower ethylenediamine slowly dripping 15g, dropwises to be warming up to 28 DEG C slowly afterwards, and stirring reaction 24h obtains the dendrimer (1.0GPAMAM) in integer generation.
2, the preparation of polystyrene seed, by emulsion dispersion polymerization synthesis particle diameter 1 ~ 3 μm of monodisperse polystyrene seed, the concentration of monomer styrene is 15% (m/m) of total amount, stabilizing agent polyvinylpyrrolidone consumption is 2% (m/v) of reaction medium, initator azodiisobutyronitrile consumption is 1% (m/m) of monomer consumption, and reaction medium is absolute ethyl alcohol, reaction temperature 60 DEG C, mixing speed at 200 revs/min, 24 hours reaction time;
3, swelling method prepares single dispersing and gathers polystyrene-divinylbenzene-GMA (PS-DVB-GMA) microballoon, the quality of monomer styrene accounts for 15% of total organic phase quality, the quality adding monomer methacrylic acid ethylene oxidic ester (GMA) is 6% of organic phase gross mass, the degree of cross linking quality m concentration being controlled complex microsphere by the consumption of adjustment cross-linker divinylbenzene is 55%, , the quality of emulsifying agent dodecyl sodium sulfate is 2% of organic phase gross mass, the quality of stabilizing agent polyvinyl alcohol accounts for 5% of gross mass, the matter of initator benzoyl peroxide is 0.4% of gross mass, the quality of toluene is 20% of total organic phase quality, controlling emulsifying temperature is 35 DEG C, swelling ratio is 30 times, reaction temperature is 70 DEG C, mixing speed is 200 turns, the reaction time polystyrene synthesized by 24h-divinylbenzene-GMA (PS-DVB-GMA) microballoon uniformity is higher, without the need to further classification or screening.
4, with polystyrene-divinylbenzene-GMA microballoon for matrix, reacted by the epoxy radicals of microsphere surface and the integer terminal amino group for dendrimer, dendrimer is grafted to microsphere surface, again with 1,4-butanediol glycidol ether Hybrid Heating, react with dendrimer terminal amino group, make terminal amido become quaternary ammonium group.The concentration of quaternizing agent BDO glycidol ether is 30%.
5, the high power capacity of dendrimer surface grafting polystyrene-divinylbenzene-GMA filler ethanol and water are cleaned namely obtain required filler, obtained filler homogenate method dress post.
6, be mobile phase with the NaOH of 20mM, adopt Suppressor conductivity detection device to detect conventional anion.
Embodiment 3:
1, integer is for the preparation of dendrimer (PAMAM), the ethylenediamine getting 2mL is dissolved in the methyl alcohol of 25mL, ice-water bath slowly adds the methyl acrylate of 25g under stirring, and dropwises slowly to be warming up to 28 DEG C afterwards, and stirring reaction 24h obtains the PAMAM of 0.5G; Getting 5g0.5GPAMAM is dissolved in 25mL methyl alcohol, and ice-water bath stirs the lower ethylenediamine slowly dripping 15g, dropwises to be warming up to 28 DEG C slowly afterwards, and stirring reaction 24h obtains the dendrimer (1.0GPAMAM) in integer generation.
2, the preparation of polystyrene seed, by emulsion dispersion polymerization synthesis particle diameter 1 ~ 3 μm of monodisperse polystyrene seed, the concentration of monomer styrene is 15% (m/m) of total amount, stabilizing agent polyvinylpyrrolidone consumption is 2% (m/v) of reaction medium, initator azodiisobutyronitrile consumption is 1% (m/m) of monomer consumption, and reaction medium is absolute ethyl alcohol, reaction temperature 60 DEG C, mixing speed at 200 revs/min, 24 hours reaction time;
3, swelling method prepares single dispersing and gathers polystyrene-divinylbenzene-GMA (PS-DVB-GMA) microballoon, the quality of monomer styrene accounts for 15% of total organic phase quality, the quality adding monomer methacrylic acid ethylene oxidic ester (GMA) is 7.5% of organic phase gross mass, the degree of cross linking quality m concentration being controlled complex microsphere by the consumption of adjustment cross-linker divinylbenzene is 55%, , the quality of emulsifying agent dodecyl sodium sulfate is 2% of organic phase gross mass, the quality of stabilizing agent polyvinyl alcohol accounts for 5% of gross mass, the matter of initator benzoyl peroxide is 0.4% of gross mass, the quality of toluene is 20% of total organic phase quality, controlling emulsifying temperature is 35 DEG C, swelling ratio is 30 times, reaction temperature is 70 DEG C, mixing speed is 200 turns, the reaction time polystyrene synthesized by 24h-divinylbenzene-GMA (PS-DVB-GMA) microballoon uniformity is higher, without the need to further classification or screening.
4, with polystyrene-divinylbenzene-GMA microballoon for matrix, reacted by the epoxy radicals of microsphere surface and the integer terminal amino group for dendrimer, dendrimer is grafted to microsphere surface, again with 1,4-butanediol glycidol ether Hybrid Heating, react with dendrimer terminal amino group, make terminal amido become quaternary ammonium group.The concentration of quaternizing agent BDO glycidol ether is 30%.
5, the high power capacity of dendrimer surface grafting polystyrene-divinylbenzene-GMA filler ethanol and water are cleaned namely obtain required filler, obtained filler homogenate method dress post.
6, be mobile phase with the NaOH of 20mM, adopt Suppressor conductivity detection device to detect conventional anion.
Embodiment 4:
1, integer is for the preparation of dendrimer (PAMAM), the ethylenediamine getting 2mL is dissolved in the methyl alcohol of 25mL, ice-water bath slowly adds the methyl acrylate of 25g under stirring, and dropwises slowly to be warming up to 28 DEG C afterwards, and stirring reaction 24h obtains the PAMAM of 0.5G; Getting 5g0.5GPAMAM is dissolved in 25mL methyl alcohol, and ice-water bath stirs the lower ethylenediamine slowly dripping 15g, dropwises to be warming up to 28 DEG C slowly afterwards, and stirring reaction 24h obtains the dendrimer (1.0GPAMAM) in integer generation.
2, the preparation of polystyrene seed, by emulsion dispersion polymerization synthesis particle diameter 1 ~ 3 μm of monodisperse polystyrene seed, the concentration of monomer styrene is 15% (m/m) of total amount, stabilizing agent polyvinylpyrrolidone consumption is 2% (m/v) of reaction medium, initator azodiisobutyronitrile consumption is 1% (m/m) of monomer consumption, and reaction medium is absolute ethyl alcohol, reaction temperature 60 DEG C, mixing speed at 200 revs/min, 24 hours reaction time;
3, swelling method prepares single dispersing and gathers polystyrene-divinylbenzene-GMA (PS-DVB-GMA) microballoon, the quality of monomer styrene accounts for 15% of total organic phase quality, the quality adding monomer methacrylic acid ethylene oxidic ester (GMA) is 9% of organic phase gross mass, the degree of cross linking quality m concentration being controlled complex microsphere by the consumption of adjustment cross-linker divinylbenzene is 55%, , the quality of emulsifying agent dodecyl sodium sulfate is 2% of organic phase gross mass, the quality of stabilizing agent polyvinyl alcohol accounts for 5% of gross mass, the matter of initator benzoyl peroxide is 0.4% of gross mass, the quality of toluene is 20% of total organic phase quality, controlling emulsifying temperature is 35 DEG C, swelling ratio is 30 times, reaction temperature is 70 DEG C, mixing speed is 200 turns, the reaction time polystyrene synthesized by 24h-divinylbenzene-GMA (PS-DVB-GMA) microballoon uniformity is higher, without the need to further classification or screening.
4, with polystyrene-divinylbenzene-GMA microballoon for matrix, reacted by the epoxy radicals of microsphere surface and the integer terminal amino group for dendrimer, dendrimer is grafted to microsphere surface, again with 1,4-butanediol glycidol ether Hybrid Heating, react with dendrimer terminal amino group, make terminal amido become quaternary ammonium group.The concentration of quaternizing agent BDO glycidol ether is 30%.
5, the high power capacity of dendrimer surface grafting polystyrene-divinylbenzene-GMA filler ethanol and water are cleaned namely obtain required filler, obtained filler homogenate method dress post.
6, be mobile phase with the NaOH of 20mM, adopt Suppressor conductivity detection device to detect conventional anion.
Embodiment 5: column performance is tested
Instrument: contain vast CIC-100 chromatograph, SHY-A-III TVS, vast conductance cell detector is contained in Qingdao
Sample: F
-(analyzing pure)
Leacheate: 10mMNaOH solution
Splitter: self-made fill post
Flow velocity: 1mL/min
Embodiment 6: column performance is tested
Instrument: contain vast CIC-100 chromatograph, SHY-A-III TVS, vast conductance cell detector is contained in Qingdao
Sample: Cl
-(analyzing pure)
Leacheate: 20mMNaOH solution
Splitter: self-made fill post
Flow velocity: 1mL/min
Fig. 3 is that self-control novel high-capacity graft type ion chromatographic column is to fluorine ion retention figure, join Qingdao contain vast conductance cell detector and SHY-A-III TVS to contain vast CIC-100 chromatograph, adopt 10mMNaOH solution as mobile phase, the strength retention of homemade ion chromatographic column to fluorine ion is detected, 1-F in chromatogram
-(3ppm) retention time is 5.6min, and compared with conventional anion chromatographic column, self-control high power capacity graft type ion chromatographic column is more of a specified duration to the retention time of fluorine ion, and better with the separating effect of system peak (water negative peak).
Fig. 4 is that novel high-capacity graft type ion chromatographic column processed is to chlorion retention figure, join Qingdao contain vast conductance cell detector and SHY-A-III TVS to contain vast CIC-100 chromatograph, adopt 20mMNaOH solution as mobile phase, the strength retention of homemade ion chromatographic column to chlorion is detected, 1-Cl in chromatogram
-(5ppm) retention time is 35.8min, is far longer than the retention time in conventional anion detection, illustrates that the present invention's homemade chromatography of ions Stationary liquid has higher column capacity.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.The invention is not restricted to embodiment here, those skilled in the art are according to announcement of the present invention, and the improvement made for the present invention and amendment all should within protection scope of the present invention.
Claims (8)
1. the preparation method of a novel graft type high power capacity dendrimer modified ion chromatographic stationary phases, it is characterized in that, adopt styrene-divinylbenzene-GMA matrix, monodispersed linear polystyrene microballoon seed is prepared with dispersion copolymerization method, adopt single step seed swelling method by polystyrene-divinylbenzene-GMA (PS-DVB-GMA) microballoon of the seed synthetic surface after activation with a large amount of epoxy radicals, extracting removing pore-foaming agent, pass through chemical graft process, Polyamidoamine Dendrimers is grafted to microsphere surface, with 1, 4-butanediol glycidol ether (BDDE) is as quaternizing agent, terminal amino group is converted into quaternary ammonium group.
2. novel graft type high power capacity dendrimer modified ion chromatographic stationary phases preparation method according to claim 1, it is characterized in that, described Polyamidoamine Dendrimers is synthesized by Micheal addition and amidation process by methyl acrylate and ethylenediamine.
3. novel graft type high power capacity dendrimer modified ion chromatographic stationary phases preparation method according to claim 1 and 2, it is characterized in that, the synthesis of described Polyamidoamine Dendrimers-amine carries out at the temperature of 20-30 DEG C.
4. novel graft type high power capacity dendrimer modified ion chromatographic stationary phases preparation method according to claim 1, it is characterized in that, in described single dispersing linear polystyrene Spawn preparation process, the mass fraction of monomer styrene is 5-30% (g/g), be stabilizing agent with polyvinylpyrrolidone and control the 0.5-4% (g/ml) that its quality accounts for reaction cumulative volume, the quality of initator azodiisobutyronitrile is the 1-5% (g/g) of monomer mass, reaction medium is the ethanol of volume fraction between 75-100%, reaction temperature is 50-80 DEG C, mixing speed controls at 100-400r/min, reaction time is 8-24h.
5. novel graft type high power capacity dendrimer modified ion chromatographic stationary phases preparation method according to claim 1, it is characterized in that, in the process of described one-step swelling method synthetic polystyrene-divinylbenzene-GMA microballoon, the quality of monomer styrene accounts for the 10-20% (g/g) of total organic phase quality, the degree of cross linking quality m change in concentration scope of complex microsphere is at 10-75% (g/ml) and by regulating the consumption of cross-linker divinylbenzene to control, the quality of emulsifying agent dodecyl sodium sulfate is the 2-4% (g/g) of organic phase gross mass, the quality of stabilizing agent polyvinyl alcohol accounts for the 0.5-5% (g/g) of gross mass, the quality of initator benzoyl peroxide is the 0.4-1.5% (g/g) of gross mass, the quality of pore-foaming agent toluene is the 20-70% (g/g) of total organic phase quality, control emulsifying temperature is 20-35 DEG C, swelling ratio is 30-70 times, reaction temperature is 60-85 DEG C, mixing speed is that 100-300 turns, reaction time is 18-48h.
6. the novel graft type high power capacity dendrimer modified ion chromatographic stationary phases preparation method according to claim 1 or 4 or 5, is characterized in that the particle diameter of described microballoon can by regulating and controlling crosslinking agent, stably dispersing agent concentration, swelling temperature, pore-foaming agent, reaction temperature, initiator concentration and swelling adjustment.
7. novel graft type high power capacity dendrimer modified ion chromatographic stationary phases preparation method according to claim 1 or 5, it is characterized in that in the process of one-step swelling method synthetic polystyrene-divinylbenzene-GMA microballoon, except styrene monomer, also add a large amount of GMA as another kind of monomer, make the polymer microballoon of synthesis surface directly with the activated epoxy radicals of a large amount of tool, the quality of GMA monomer is the 6-9% of organic phase gross mass.
8. novel graft type high power capacity dendrimer modified ion chromatographic stationary phases preparation method according to claim 1, it is characterized in that described Polyamidoamine Dendrimers is by the epoxy reaction direct grafting a large amount of with base ball surface, again with quaternizing agent 1,4-butanediol glycidol ether Hybrid Heating reacts the quaternized ammonium groups making Polyamidoamine Dendrimers terminal amino group become positively charged, concentration wherein for the BDO glycidol ether reacted is 10-30%.
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