CN104945631A - Preparation method of novel grafted dendritic macromolecular microspheres - Google Patents
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Abstract
The invention discloses a preparation method of novel grafted dendritic macromolecular microspheres and provides a preparation method of a first generation (1.0G) dendritic macromolecular grafted ion chromatography stationary phase. The preparation method comprises the preparation of 1.0G dendritic macromolecules, the preparation of polystyrene-divinylbenze microspheres, the grafting of the dendritic macromolecules and the microspheres, the quaternarization modification of the dendritic macromolecules and the preparation of a quaternarized dendritic macromolecule grafted anionic chromatography filler. According to the method, the dendritic structure of the dendritic macromolecular is thoroughly utilized to modify the surface of the microspheres, the reaction is fast, the period is short and the method is simple and convenient, and the synthesized filler is excellent in properties.
Description
Technical field
The present invention relates to a kind of preparation method of chromatography of ions, particularly relate to the preparation method of novel graft type dendrimer microballoon, the application of first-generation dendrimer material in the preparation of surface-grafted type chromatography of ions filler.
Background technology
Chromatography of ions filler is as one of core composition affecting ion chromatographic separation effect, and two, the ion position part primarily of insoluble matrix and stationary phase forms.Wherein, matrix can be divided into organic substrate and inorganic matrix two kinds, and stationary phase ion position is mainly through having come the chemically modified of stationary phase.Main chemical modification method has: chemical graft process, surperficial agglomeration technique and microsphere surface direct reaction are modified.At present, in the chromatography of ions modifying method that we often adopt, limiting to a number or amount that the ionic sites that surperficial agglomeration technique and microsphere surface direct reaction are modified is amassed by microsphere surface is limited, is difficult to improve post effect further
[1]if go for the stationary phase of more heavy body, only have and obtain more ionic sites by Graft Method in layer grafting, and this method is by repeatedly reacting, in layer grafting, process is very complicated
[2].
Compared with liquid chromatography stuffing, still there is very large deficiency in chromatography of ions filler, along with further developing of chromatography of ions filler, the performance of stationary phase needs to be improved further, except the exploitation of kapillary, monoblock type, ultra-high voltage and High temperature ion chromatographic stationary phases, novel material and more convenient effective modifying method also will play huge effect improving chromatography of ions stationary phase aspect of performance.
Reference:
1. peaceful monarch, punishment grain husk, Hou little Ping, Kong Fanzuo, Mu Shifen, the development of surperficial agglomeration thin shell type single dispersing high-effective cationic chromatographic column packing material and chromatographic property thereof, chromatogram, 2002,20:530-533
2.Z-P.Huang,H-W.Wu,F-L.Wang,W-W.Yan,W-Q.Guo,Y.Zhu,Polystyrene-divinylbenzene stationary phases agglomerated with quaternized multi-walled carbon nanotubes for anion exchange chromatography,J.Chromatogr.A,2013,1294:152-156
Summary of the invention
The preparation method of the present invention to graft type chromatographic stationary phases improves, the preparation method of the novel surface graft type anion chromatographic stationary phase providing a kind of dendrimer to modify, the present invention makes full use of the hyperbranched structure of dendrimer, there is preparation technology simple, synthesis cycle is short, filler sphere diameter is even, the advantages such as column capacity is higher, resistance to acids and bases.
The present invention is achieved through the following technical solutions:
The invention discloses the preparation method of a kind of novel grafting or agglomeration type dendrimer microballoon, preparation method comprises the preparation of 1.0G dendrimer, the preparation of polystyrene divinylbenzene microballoon, the grafting of dendrimer and microballoon, the quaternized modification of dendrimer and the preparation of quaternized dendrimer graft type anion chromatographic filling material, take polystyrene-divinylbenzene as matrix, dispersion copolymerization method is adopted to prepare monodispersed linear polystyrene microballoon seed, after seed activation, adopt single step seed swelling method, synthetic polystyrene-divinylbenzene microspheres, extracting removing pore-creating agent, pass through chemical graft process again, 1.0G polyamide-amide (PAMAM) dendrimer is grafted to microsphere surface and adopts 1, 4-butyleneglycol glycidyl ether is to its quaternized modification, with homogenate method dress post.
Concrete preparation process of the present invention is:
A. divergent method is adopted to prepare 1.0GPAMAM dendrimer
Take quadrol as core, generate with-COCH with methyl acrylate Micheal addition
3for the PAMAM of the 0.5G of end, then with quadrol generation amidate action, further generating end is-NH
2the PAMAM of 1.0G;
B. dispersion copolymerization method is adopted to synthesize monodispersed linear polystyrene microballoon seed
Take vinylbenzene as monomer, polystyrene pyrrolidone is as stablizer, and Diisopropyl azodicarboxylate is as initiator, monodispersed linear polystyrene microballoon seed is generated by radical polymerization in the blending agent of second alcohol and water, seed particle size is between 1-3 μm, and uniform particle sizes, without the need to classification;
C. one-step swelling method synthetic polystyrene-divinylbenzene microspheres is adopted
The single dispersing linear polymerization phenylethylene micro ball of synthesis is mixed with dibutyl phthalate and makes seed activation, add monomer styrene subsequently, cross-linker divinylbenzene, emulsifying agent sodium laurylsulfonate, stablizer polyvinyl alcohol, initiator benzoyl peroxide and pore-creating agent toluene carry out swelling; Then add thermal booster reaction and make monomer polymerization, prepare monodispersed polystyrene-divinylbenzene microspheres, the polymer microballoon of gained extracts de-emulsifier and stablizer with toluene again;
D. Graft Method is adopted to modify polystyrene-divinylbenzene microspheres and carry out quaternary ammonium modification
The microballoon of preparation and glycidyl methacrylate are reacted, epoxide group is introduced at microsphere surface, 1.0G dendrimer is fully mixed with the microballoon of surface with epoxy group(ing), add thermal booster reaction, clean with deionized water wash subsequently, then add quaternizing agent BDO glycidyl ether, add thermal booster reaction, by clean for product deionized water wash.
As improving further, in the preparation process of described PAMAM dendrimer, the PAMAM molar ratio of synthesis 0.5G is 1:8; The PAMAM molar ratio of synthesis 1.0G is 1:24.
As improving further, in the preparation process of described single dispersing linear polystyrene microballoon seed, the massfraction of monomer styrene is 5-30%, stablizer polyvinylpyrrolidone quality account for the 0.5-4% of total reaction volume, the quality of initiator Diisopropyl azodicarboxylate is the 1-5% of monomer mass, take ethanol as reaction medium, its volumetric concentration is 75-100%, temperature of reaction is 40-85 DEG C, and stirring velocity controls at 100-400r/min, and the reaction times is 8-24h.
As improving further, in the process of described one-step swelling method synthetic polystyrene-divinylbenzene microspheres, monomer styrene quality control is at the 10-20% of total organic phase quality, the degree of crosslinking quality m change in concentration scope of complex microsphere is controlled at 10-75% by regulating the consumption of cross-linker divinylbenzene, the quality of emulsifying agent sodium laurylsulfonate accounts for the 2-4% of organic phase total mass, the quality of stablizer polyvinyl alcohol and initiator benzoyl peroxide is respectively 0.5-5% and 0.4-1.5% of total mass, the quality of pore-creating agent toluene is the 20-70% of total organic phase quality, emulsifying temperature is 20-35 DEG C, swelling ratio is 30-70 times, temperature of reaction is 60-85 DEG C, stirring velocity is that 100-300 turns, reaction times is 12-48h, the particle size range of synthesized polystyrene divinylbenzene microballoon is between 6-8 μm.
As improving further, the particle diameter of the microballoon of described method synthesis can be regulated and controled by the selection of pore-creating agent, linking agent, dispersion stabilizer solubility, swelling temperature, temperature of reaction, initiator concentration or swelling ratio.
As improving further, described dendrimer by with glycidyl methacrylate reactive grafting in the process on the surface of base ball, the unsaturated link(age) of microsphere surface remnants and methyl propenoic acid glycidyl ether is utilized to react, make microsphere surface with epoxy group(ing), in 1 generation dendrimer (1.0GPAMAM), is surperficial to base ball by the reactive grafting of terminal amino group and base ball surface epoxy group(ing), the quaternized ammonium groups making dendrimer terminal amino group become positively charged is reacted again with quaternizing agent BDO glycidyl ether Hybrid Heating.
As improving further, be 10-30% in the described concentration for the BDO glycidyl ether reacted.
As improving further, the chromatography of ions filler that the present invention is prepared at described dendrimer Graft Method can realize F
-, Cl
-, Br
-, NO
2-, NO
3-, SO
4 2-effective separation of ion.
Tool of the present invention has the following advantages:
1, the packed art prepared of the preparation method of polystyrene-divinylbenzene microspheres provided by the invention is simple, cost is low, long service life, uniform particle sizes, and chemical stability is better, can tolerate wider pH tolerance range.
2, the preparation method of generation dendrimer graft type chromatography of ions stationary phase provided by the invention, by the regulation and control to dendrimer branched structure, can realize the strict control to chromatographic stationary phases performance, retention time, strength retention and column capacity.
3, the chromatography of ions stationary phase of generation dendrimer Graft Method modification provided by the invention, surface group grafting is firm, and acid and alkali-resistance, stable chemical nature, ensure that column performance is more stable, longer service life is of a specified duration.
4, the preparation method of generation dendrimer graft type chromatography of ions stationary phase provided by the invention, the branch-like structure of abundant dendrimer, on the basis of chromatographic column modifying method in the past, further increase column capacity and post effect, water negative peak and fluorion in general agglomeration type chromatography of ions can be solved and be difficult to the historic problem be separated.
5, the preparation method of generation dendrimer graft type chromatography of ions stationary phase provided by the invention, the branched structure of dendrimer can be made full use of, the preparation of the chromatography of ions fixed phase stuffing of higher column capacity is realized by the method for a step grafting, avoid the trouble of grafting layer by layer in traditional Graft Method modification, the anion chromatographic fixed phase stuffing not only good stability of preparation, the pH of relative broad range can be tolerated, and Common Anions can be realized as F
-, Cl
-, Br
-, NO
2-, NO
3-, SO
4 2-effective separation.
Accompanying drawing explanation
Fig. 1 is fixed phase stuffing infrared spectrogram after modifying, and has obvious phenyl ring (1450-1650cm in spectrogram
-1), C=O (1700cm
-1), C-N (1150cm
-1) and N-H (3400cm
-1) absorption peak, at the end-NH that 3000-3500cm-1 does not have obvious bimodal explanation not dissociate
2, all terminal amino groups are all quaternized and exist with the form of quaternary ammonium salt;
Fig. 2 is the color atlas of conventional anion, joins Qingdao and contains vast conductivity cell detector and SHY-A-III suppressor, carry out Performance Detection, 1-F in color atlas to homemade ion chromatographic column to contain vast CIC-100 chromatographic instrument
-(3ppm), 2-Cl
-(5ppm), Br
-(20ppm), NO
2-(15ppm), NO
3-(20ppm), SO
4 2-(ppm) good baseline separation can be obtained, the testing requirement of quantitative and qualitative analysis can be met.
Embodiment
The invention discloses a kind of preparation method of dendrimer graft type chromatography of ions stationary phase, comprise: the preparation of 1.0G dendrimer, the preparation of polystyrene divinylbenzene microballoon, the grafting of dendrimer and microballoon, the quaternized modification of dendrimer and the preparation of quaternized dendrimer graft type anion chromatographic filling material, take polystyrene-divinylbenzene as matrix, dispersion copolymerization method is adopted to prepare monodispersed linear polystyrene microballoon seed, after seed activation, adopt single step seed swelling method, synthetic polystyrene-divinylbenzene microspheres, extracting removing pore-creating agent.Again by chemical graft process, polyamide-amide (PAMAM) dendrimer is grafted to microsphere surface and adopts BDO glycidyl ether to its quaternized modification; With homogenate method dress post, concrete preparation process is:
A. divergent method is adopted to prepare 1.0GPAMAM dendrimer
Take quadrol as core, generate with-COCH with methyl acrylate Micheal addition
3for the PAMAM of the 0.5G of end, then with quadrol generation amidate action, further generating end is-NH
2the PAMAM of 1.0G.
B. dispersion copolymerization method is adopted to synthesize monodispersed linear polystyrene microballoon seed
Take vinylbenzene as monomer, polystyrene pyrrolidone is as stablizer, and Diisopropyl azodicarboxylate is as initiator, second alcohol and water and generate monodispersed linear polystyrene microballoon seed by radical polymerization in blending agent, seed particle size is between 1-3 μm, and uniform particle sizes, without the need to classification;
C. one-step swelling method synthetic polystyrene-divinylbenzene microspheres is adopted
Being mixed with dibutyl phthalate by the single dispersing linear polymerization phenylethylene micro ball of synthesis makes seed activation add monomer styrene subsequently, cross-linker divinylbenzene, emulsifying agent sodium laurylsulfonate, stablizer polyvinyl alcohol, initiator benzoyl peroxide and pore-creating agent toluene carry out swelling; Then add thermal booster reaction and make monomer polymerization, prepare monodispersed polystyrene-divinylbenzene microspheres, the polymer microballoon of gained extracts de-emulsifier and stablizer with toluene again.
D. Graft Method is adopted to modify polystyrene-divinylbenzene microspheres and carry out quaternary ammonium modification
The microballoon of preparation and glycidyl methacrylate are reacted, epoxide group is introduced at microsphere surface, 1.0G dendrimer is fully mixed with the microballoon of surface with epoxy group(ing), add thermal booster reaction, clean with deionized water wash subsequently, then add quaternizing agent BDO glycidyl ether, add thermal booster reaction, by clean for product deionized water wash.
In the preparation of single dispersing linear polystyrene microballoon seed, the massfraction of monomer styrene is 5-30%, stablizer polyvinylpyrrolidone quality account for the 0.5-4% of total reaction volume, the quality of initiator Diisopropyl azodicarboxylate is the 1-5% of monomer mass, take ethanol as reaction medium, its volumetric concentration is 75-100%, and temperature of reaction is 40-85 DEG C, stirring velocity controls at 100-400r/min, and the reaction times is 8-24h.In the process of one-step swelling method synthetic polystyrene-divinylbenzene microspheres, monomer styrene quality control is at the 10-20% of total organic phase quality, the degree of crosslinking quality m change in concentration scope of complex microsphere is controlled at 10-75% by regulating the consumption of cross-linker divinylbenzene, the quality of emulsifying agent sodium laurylsulfonate accounts for the 2-4% of organic phase total mass, the quality of stablizer polyvinyl alcohol and initiator benzoyl peroxide is respectively 0.5-5% and 0.4-1.5% of total mass, the quality of pore-creating agent toluene is the 20-70% of total organic phase quality, emulsifying temperature is 20-35 DEG C, swelling ratio is 30-70 times, temperature of reaction is 60-85 DEG C, stirring velocity is that 100-300 turns, reaction times is 12-48h, the particle size range of synthesized polystyrene divinylbenzene microballoon is between 6-8 μm, and homogeneity is higher, without the need to further classification or screening.The particle diameter of synthesis microballoon can be regulated and controled by the selection of pore-creating agent, linking agent, dispersion stabilizer solubility, swelling temperature, temperature of reaction, initiator concentration or swelling ratio.In grafting method, dendrimer by with the surface of glycidyl methacrylate reactive grafting to base ball.The unsaturated link(age) of microsphere surface remnants and methyl propenoic acid glycidyl ether is utilized to react, make microsphere surface with epoxy group(ing), in 1 generation dendrimer (1.0GPAMAM), is surperficial to base ball by the reactive grafting of terminal amino group and base ball surface epoxy group(ing), again with quaternizing agent 1,4-butyleneglycol glycidyl ether Hybrid Heating reacts the quaternized ammonium groups making dendrimer terminal amino group become positively charged, concentration wherein for the BDO glycidyl ether reacted is 10-30%.Modifying method avoids the drawback that traditional modifying method needs grafting layer by layer, and the chromatogram can preparing heavy body fast exchanges filler.Chromatography of ions filler prepared by dendrimer Graft Method can realize F
-, Cl
-, Br
-, NO
2-, NO
3-, SO
4 2-effective separation of ion, compared with latex agglomeration type chromatography of ions stationary phase, fluorion also can be separated preferably with water negative peak.
Below by specific embodiment, technical scheme of the present invention is described in further detail:
The preparation process of embodiment 1:1.0GPAMAM graft type polystyrene-divinylbenzene anion chromatographic fixed phase stuffing is as follows, the steps include:
1, the preparation of 0.5GPAMAM, the quadrol getting 2mL is dissolved in the methyl alcohol of 20mL, and ice-water bath slowly adds the methyl acrylate of 23g under stirring, and dropwises slowly to be warming up to 25 DEG C afterwards, and stirring reaction 24h obtains the PAMAM of 0.5G.
2, the preparation of 1.0GPAMAM, gets 5g0.5GPAMAM and is dissolved in 20mL methyl alcohol, and ice-water bath stirs the lower quadrol slowly dripping 15g, dropwises to be warming up to 25 DEG C slowly afterwards, and stirring reaction 24h obtains the PAMAM of 0.5G.
3, 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 5% (m/m) of total amount, stablizer polyvinylpyrrolidone consumption is 0.5% (m/v) of reaction medium, initiator Diisopropyl azodicarboxylate consumption is 1 (m/m) of monomer consumption, reaction medium is aqueous ethanolic solution, concentration is 75% (v/v), temperature of reaction 70 DEG C, stirring velocity at 250 revs/min, 24 hours reaction times;
4, swelling method prepares monodisperse polystyrene one divinylbenzene microspheres, monomer styrene quality control is 10% of total organic phase quality, the degree of crosslinking quality m change in concentration scope of complex microsphere is controlled 45% by regulating the consumption of cross-linker divinylbenzene, the quality of emulsifying agent sodium laurylsulfonate accounts for 2% of organic phase total mass, the quality of stablizer polyvinyl alcohol and initiator benzoyl peroxide is respectively 0.5% and 0.4% of total mass, the quality of pore-creating agent toluene is 20% of total organic phase quality, quality for the glycidyl methacrylate of surface grafting is 2% of total mass, emulsifying temperature is 25 DEG C, swelling ratio is 70 times, temperature of reaction is 70 DEG C, stirring velocity is 200 turns, reaction times is 24h, synthesized polystyrene-Vinylstyrene-glycidyl methacrylate (PS-DVB-GMA) microballoon homogeneity is higher, without the need to further classification or screening.
5, with polystyrene-Vinylstyrene-glycidyl methacrylate microballoon for matrix, reacted by the epoxy group(ing) of microsphere surface and 1.0GPAMAM terminal amino group, the dendrimer of 1.0G is grafted to microsphere surface, again with 1,4-butyleneglycol glycidyl ether is quaternizing agent, react with dendrimer terminal amino group, it is quaternized.The concentration of quaternizing agent BDO glycidyl ether is 10%.
6, the polystyrene-Vinylstyrene-glycidyl methacrylate filler ethanol of dendrimer surface grafting and water are cleaned namely obtain required filler, obtained filler homogenate method dress post.
7, be moving phase with the NaOH of 10mM, adopt Suppressor conductivity detection device to detect conventional anion.
Embodiment 2: with reference to method and the step of embodiment 1
1, the preparation of 0.5GPAMAM, the quadrol getting 2mL is dissolved in the methyl alcohol of 20mL, and ice-water bath slowly adds the methyl acrylate of 23g under stirring, and dropwises slowly to be warming up to 25 DEG C afterwards, and stirring reaction 24h obtains the PAMAM of 0.5G.
2, the preparation of 1.0GPAMAM, gets 5g0.5GPAMAM and is dissolved in 20mL methyl alcohol, and ice-water bath stirs the lower quadrol slowly dripping 15g, dropwises to be warming up to 25 DEG C slowly afterwards, and stirring reaction 24h obtains the PAMAM of 0.5G.
3, 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 5% (m/m) of total amount, stablizer polyvinylpyrrolidone consumption is 0.5% (m/v) of reaction medium, initiator Diisopropyl azodicarboxylate consumption is 1% (m/m) of monomer consumption, reaction medium is aqueous ethanolic solution, concentration is 75% (v/v), temperature of reaction 70 DEG C, stirring velocity at 250 revs/min, 24 hours reaction times;
4, swelling method prepares monodisperse polystyrene one divinylbenzene microspheres, monomer styrene quality control is 10% of total organic phase quality, the degree of crosslinking quality m change in concentration scope of complex microsphere is controlled 45% by regulating the consumption of cross-linker divinylbenzene, the quality of emulsifying agent sodium laurylsulfonate accounts for 2% of organic phase total mass, the quality of stablizer polyvinyl alcohol and initiator benzoyl peroxide is respectively 0.5% and 0.4% of total mass, the quality of pore-creating agent toluene is 20% of total organic phase quality, quality for the glycidyl methacrylate of surface grafting is 2% of total mass, emulsifying temperature is 25 DEG C, swelling ratio is 70 times, temperature of reaction is 70 DEG C, stirring velocity is 250 turns, reaction times is 24h, synthesized polystyrene-Vinylstyrene-glycidyl methacrylate (PS-DVB-GMA) microballoon homogeneity is higher, without the need to further classification or screening.
5, with polystyrene-Vinylstyrene-glycidyl methacrylate microballoon for matrix, reacted by the epoxy group(ing) of microsphere surface and 1.0GPAMAM terminal amino group, the dendrimer of 1.0G is grafted to microsphere surface, again with 1,4-butyleneglycol glycidyl ether is quaternizing agent, react with dendrimer terminal amino group, it is quaternized.The concentration of quaternizing agent BDO glycidyl ether is 20%.
6, the polystyrene-Vinylstyrene-glycidyl methacrylate filler ethanol of dendrimer surface grafting and water are cleaned namely obtain required filler, obtained filler homogenate method dress post.
7, be moving phase with the NaOH of 10mM, adopt Suppressor conductivity detection device to detect conventional anion.
Embodiment 3:
1, the preparation of 0.5GPAMAM, the quadrol getting 2mL is dissolved in the methyl alcohol of 20mL, and ice-water bath slowly adds the methyl acrylate of 23g under stirring, and dropwises slowly to be warming up to 25 DEG C afterwards, and stirring reaction 24h obtains the PAMAM of 0.5G.
2, the preparation of 1.0GPAMAM, gets 5g0.5GPAMAM and is dissolved in 20mL methyl alcohol, and ice-water bath stirs the lower quadrol slowly dripping 15g, dropwises to be warming up to 25 DEG C slowly afterwards, and stirring reaction 24h obtains the PAMAM of 0.5G.
3, 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 5% (m/m) of total amount, stablizer polyvinylpyrrolidone consumption is 0.5% (m/v) of reaction medium, initiator Diisopropyl azodicarboxylate consumption is 1% (m/m) of monomer consumption, reaction medium is aqueous ethanolic solution, concentration is 75% (v/v), temperature of reaction 70 DEG C, stirring velocity at 250 revs/min, 24 hours reaction times;
4, swelling method prepares monodisperse polystyrene one divinylbenzene microspheres, monomer styrene quality control is 10% of total organic phase quality, the degree of crosslinking quality m change in concentration scope of complex microsphere is controlled 45% by regulating the consumption of cross-linker divinylbenzene, the quality of emulsifying agent sodium laurylsulfonate accounts for 2% of organic phase total mass, the quality of stablizer polyvinyl alcohol and initiator benzoyl peroxide is respectively 0.5% and 0.4% of total mass, the quality of pore-creating agent toluene is 20% of total organic phase quality, quality for the glycidyl methacrylate of surface grafting is 2% of total mass, emulsifying temperature is 25 DEG C, swelling ratio is 70 times, temperature of reaction is 70 DEG C, stirring velocity is 250 turns, reaction times is 24h, synthesized polystyrene-Vinylstyrene-glycidyl methacrylate (PS-DVB-GMA) microballoon homogeneity is higher, without the need to further classification or screening.
5, with polystyrene-Vinylstyrene-glycidyl methacrylate microballoon for matrix, reacted by the epoxy group(ing) of microsphere surface and 1.0GPAMAM terminal amino group, the dendrimer of 1.0G is grafted to microsphere surface, again with 1,4-butyleneglycol glycidyl ether is quaternizing agent, react with dendrimer terminal amino group, it is quaternized.The concentration of quaternizing agent BDO glycidyl ether is 30%.
6, the polystyrene-Vinylstyrene-glycidyl methacrylate filler ethanol of dendrimer surface grafting and water are cleaned namely obtain required filler, obtained filler homogenate method dress post.
7, be moving phase with the NaOH of 10mM, adopt Suppressor conductivity detection device to detect conventional anion.
Embodiment 4: column performance is tested
Instrument: contain vast CIC-100 chromatographic instrument, SHY-A-III suppressor, vast conductivity cell detector is contained in Qingdao
Sample: F
-, Cl
-, Br
-, NO
2-, NO
3-, SO
4 2-(analytical pure)
Leacheate: NaOH solution
Separator column: self-made fill post
Flow velocity: 1mL/min
See the color atlas of accompanying drawing 2 conventional anion, 1-F in color atlas
-(3ppm), 2-Cl
-(5ppm), Br
-(20ppm), NO
2-(15ppm), NO
3-(20ppm), SO
4 2-(10ppm).
Finally, it is also to be noted that what enumerate above is only several specific embodiment of the present invention; obviously, the invention is not restricted to above embodiment, many distortion can also be had; as long as all distortion that disclosed content directly derives or associates, protection scope of the present invention all should be thought.
Claims (10)
1. the preparation method of a novel grafting or agglomeration type dendrimer microballoon, it is characterized in that: described preparation method comprises the preparation of 1.0G dendrimer, the preparation of polystyrene divinylbenzene microballoon, the grafting of dendrimer and microballoon, the quaternized modification of dendrimer and the preparation of quaternized dendrimer graft type anion chromatographic filling material, take polystyrene-divinylbenzene as matrix, dispersion copolymerization method is adopted to prepare monodispersed linear polystyrene microballoon seed, after seed activation, adopt single step seed swelling method, synthetic polystyrene-divinylbenzene microspheres, extracting removing pore-creating agent, pass through chemical graft process again, 1.0G polyamide-amide (PAMAM) dendrimer is grafted to microsphere surface and adopts 1, 4-butyleneglycol glycidyl ether is to its quaternized modification, with homogenate method dress post.
2. the preparation method of grafting according to claim 1 or agglomeration type dendrimer microballoon, is characterized in that: concrete preparation process is:
A. divergent method is adopted to prepare 1.0GPAMAM dendrimer
Take quadrol as core, generate with-COCH with methyl acrylate Micheal addition
3for the PAMAM of the 0.5G of end, then with quadrol generation amidate action, further generating end is-NH
2the PAMAM of 1.0G;
B. dispersion copolymerization method is adopted to synthesize monodispersed linear polystyrene microballoon seed
Take vinylbenzene as monomer, polystyrene pyrrolidone is as stablizer, and Diisopropyl azodicarboxylate is as initiator, monodispersed linear polystyrene microballoon seed is generated by radical polymerization in the blending agent of second alcohol and water, seed particle size is between 1-3 μm, and uniform particle sizes, without the need to classification;
C. one-step swelling method synthetic polystyrene-divinylbenzene microspheres is adopted
The single dispersing linear polymerization phenylethylene micro ball of synthesis is mixed with dibutyl phthalate and makes seed activation, add monomer styrene subsequently, cross-linker divinylbenzene, emulsifying agent sodium laurylsulfonate, stablizer polyvinyl alcohol, initiator benzoyl peroxide and pore-creating agent toluene carry out swelling; Then add thermal booster reaction and make monomer polymerization, prepare monodispersed polystyrene-divinylbenzene microspheres, the polymer microballoon of gained extracts de-emulsifier and stablizer with toluene again;
D. Graft Method is adopted to modify polystyrene-divinylbenzene microspheres and carry out quaternary ammonium modification
The microballoon of preparation and glycidyl methacrylate are reacted, epoxide group is introduced at microsphere surface, 1.0G dendrimer is fully mixed with the microballoon of surface with epoxy group(ing), add thermal booster reaction, clean with deionized water wash subsequently, then add quaternizing agent BDO glycidyl ether, add thermal booster reaction, by clean for product deionized water wash.
3. the preparation method of grafting according to claim 1 and 2 or agglomeration type dendrimer microballoon, is characterized in that: in the preparation process of described PAMAM dendrimer, and the PAMAM molar ratio of synthesis 0.5G is 1:8; The PAMAM molar ratio of synthesis 1.0G is 1:24.
4. the preparation method of grafting according to claim 3 or agglomeration type dendrimer microballoon, it is characterized in that: in the preparation process of described single dispersing linear polystyrene microballoon seed, the massfraction of monomer styrene is 5-30%, stablizer polyvinylpyrrolidone quality account for the 0.5-4% of total reaction volume, the quality of initiator Diisopropyl azodicarboxylate is the 1-5% of monomer mass, take ethanol as principal reaction medium, its volumetric concentration is 75-100%, temperature of reaction is 40-85 DEG C, stirring velocity controls at 100-400r/min, and the reaction times is 8-24h.
5. the preparation method of the grafting according to claim 1 or 2 or 4 or agglomeration type dendrimer microballoon, it is characterized in that: in the process of described one-step swelling method synthetic polystyrene-divinylbenzene microspheres, monomer styrene quality control is at the 10-20% of total organic phase quality, the degree of crosslinking quality m change in concentration scope of complex microsphere is controlled at 10-75% by regulating the consumption of cross-linker divinylbenzene, the quality of emulsifying agent sodium laurylsulfonate accounts for the 2-4% of organic phase total mass, the quality of stablizer polyvinyl alcohol and initiator benzoyl peroxide is respectively 0.5-5% and 0.4-1.5% of total mass, the quality of pore-creating agent toluene is the 20-70% of total organic phase quality, emulsifying temperature is 20-35 DEG C, swelling ratio is 30-70 times, temperature of reaction is 60-85 DEG C, stirring velocity is that 100-300 turns, reaction times is 12-48h, the particle size range of synthesized polystyrene divinylbenzene microballoon is between 6-8 μm.
6. the preparation method of grafting according to claim 5 or agglomeration type dendrimer microballoon, is characterized in that: the particle diameter of the microballoon of described method synthesis can be regulated and controled by the selection of pore-creating agent, linking agent, dispersion stabilizer solubility, swelling temperature, temperature of reaction, initiator concentration or swelling ratio.
7. the grafting according to claim 1 or 2 or 4 or 6 or the preparation method of agglomeration type dendrimer microballoon, it is characterized in that: described dendrimer by with glycidyl methacrylate reactive grafting in the process on the surface of base ball, the unsaturated link(age) of microsphere surface remnants and methyl propenoic acid glycidyl ether is utilized to react, make microsphere surface with epoxy group(ing), in 1 generation dendrimer (1.0GPAMAM), is surperficial to base ball by the reactive grafting of terminal amino group and base ball surface epoxy group(ing), again with quaternizing agent 1, 4-butyleneglycol glycidyl ether Hybrid Heating reacts the quaternized ammonium groups making dendrimer terminal amino group become positively charged.
8. the preparation method of grafting according to claim 7 or agglomeration type dendrimer microballoon, is characterized in that: the described concentration for the BDO glycidyl ether reacted is 10-30%.
9. the preparation method of grafting or agglomeration type dendrimer microballoon according to claim 1 or 2 or 4 or 6 or 8, is characterized in that: chromatography of ions filler prepared by described dendrimer Graft Method can realize F
-, Cl
-, Br
-, NO
2-, NO
3-, SO
4 2-effective separation of ion.
10. the preparation method of grafting or agglomeration type dendrimer microballoon according to claim 7, is characterized in that: chromatography of ions filler prepared by described dendrimer Graft Method can realize F
-, Cl
-, Br
-, NO
2-, NO
3-, SO
4 2-effective separation of ion.
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