CN104945637A - Method for preparing grafting type strong preservation anion chromatographic packing - Google Patents
Method for preparing grafting type strong preservation anion chromatographic packing Download PDFInfo
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- CN104945637A CN104945637A CN201510351526.9A CN201510351526A CN104945637A CN 104945637 A CN104945637 A CN 104945637A CN 201510351526 A CN201510351526 A CN 201510351526A CN 104945637 A CN104945637 A CN 104945637A
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- divinylbenzene
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Abstract
The method provides a method for preparing grafting type strong preservation anion chromatographic packing made of polymer polystyrene-divinyl benzene-glycidyl methacrylate-dendrimer-2,3-glycidyl trimethyl ammonium chloride. The method comprises the steps of grafting polyamide-amine dendrimer compound to polymer base ball polystyrene-divinyl benzene-glycidyl methacrylate in a grafted mode, using active cationic reagent 2,3-glycidyl trimethyl ammonium chloride to perform quaterisation modification on the grafting type base ball, and obtaining quaternary ammonium type ion chromatographic column packing having high preservation effects on anions. The obtained quaternary ammonium type ion chromatographic packing undergoes packing through a homogenate method, and an obtained compound strong preservation anion chromatographic column has very high separation preservation effects on conventional anions such as F- and Cl- and organic acids such as oxalic acid.
Description
Technical field
The present invention relates to anion chromatographic column of a kind of strong conservative and preparation method thereof, the Grafting to graft type that particularly one relates to superpolymer (PSt-DVB-GMA)-dendrimer-EPTAC retains by force the preparation method of anion chromatographic filling material, and active cation reagent E PTAC, the macromolecular material dendrimer PAMAM application method in chromatograph packing material preparation.
Background technology
Chromatography of ions is one of branch most widely used, with fastest developing speed in current stratographic analysis field, and chromatography of ions belongs to the one of high performance liquid chromatography, and it is a kind of chromatogram analysis method of analytic routines zwitterion, has superior sensitivity, selectivity.Chromatography of ions has now become the effective tool of the carbohydrate, amino acid, peptide, protein etc. analyzed in anions and canons and partial organic substances and biological sample.Along with the continuous maturation of ion chromatography, its range of application also constantly expands, and is now widely used at environmental monitoring, electric power and energy industry, food beverage industry, electron trade, life science, chemical industry and pharmaceutical industry etc.
Chromatography of ions optionally changes the character depending primarily on stationary phase to different ions.The stationary phase of chromatography of ions is made up of two portions: one is insoluble medium carrier.Matrix determines size and the distribution of filler, the intensity of filler particles, pore radiuses and distribution, and the rigidity of filling-material structure and stability etc., the textural property of matrix also determines the enforcement of chemical modification method.The matrix of filler mainly includes organic polymer matrix and inorganic matrix (silica gel, aluminum oxide use more) two large classes.Silica filler is only applicable to pH2 ~ 8, and the weakness of acid and alkali-resistance does not limit its development.Organic polymer matrix can tolerate very wide pH scope (pH0 ~ 14), available strong acid or highly basic make leacheate, make to like that compound such as carbohydrate, amino acid, organic acid, the organic amine etc. not easily dissociated change negatively charged ion or positively charged ion at neutrallty condition, thus exchange separation by ion chromatographic column.Two is combinations of matrix and functional group.The combination of matrix and functional group comprises covalent bonds, as carried out direct ion modification on surface; Surface agglomeration refers to that the individual layer latex with function machine is attached to the conjunction of matrix microspheres surface ion bond with electrostatic force; Surface-grafted type is by having the compound of macromolecule by chemical reaction and substrate-bound, then by modifying macromole.
The functional group of cation-exchange chromatography filler mainly contains sulfonic group, carboxylic acid group, phosphonate group, the functional group mainly quaternary ammonium group of anion-exchange chromatography filler.
The substrate material of anionresin stationary phase mainly contains the matrix such as styrene diethylene benzene copoly mer (PSt-DVB), vinyl xylene, ethyl vinyl benzene-divinyl benzene copolymer (EVB-DVB), polymethacrylate and polyethylene polymer.Styrene diethylene benzene copoly mer (PSt-DVB) is important anionresin stationary phase substrate material.
Summary of the invention
The invention provides a kind of superpolymer base ball polystyrene-divinylbenzene-glycidyl methacrylate (PSt-DVB-GMA) Grafting to Graft Method grafting dendrimer (PAMAM), again with active cation reagent 2,3-epoxypropyltrimethylchloride chloride (EPTAC) carries out quaternized modification to this compound graft type base ball, obtains the method for the quaternary ammonium type anion chromatographic column filler with strong retention.The quaternary ammonium type anion chromatographic column of the compound strong reservation prepared is to F
-, Cl
-deng organic acids such as conventional anion and grass, there is extremely strong retention and separation performance.
The present invention is achieved by the following technical solutions:
The invention discloses a kind of superpolymer polystyrene-divinylbenzene-glycidyl methacrylate-dendrimer-2, the graft type of 3-epoxypropyltrimethylchloride chloride retains by force the preparation method of anion chromatographic filling material, with polystyrene-divinylbenzene-glycidyl methacrylate for matrix, with quadrol and methyl acrylate for substrate, synthesized the Polyamidoamine Dendrimers of different algebraically by the Michael reaction of alternate cycles and ammonolysis reaction; The Graft Method of " being grafted to " mode of employing, at polystyrene-divinylbenzene-glycidyl glyceryl ester microsphere surface, grafting has the Polyamidoamine Dendrimers of multiple amido end chain; Again with active cation reagent 2,3-epoxypropyltrimethylchloride chloride carries out quaternized modification to the Polyamidoamine Dendrimers be grafted on polystyrene-divinylbenzene-glycidyl methacrylate microballoon, thus obtain the chromatography of ions filler with strong retention, with homogenate method dress post.
As improving further, concrete preparation process of the present invention is:
1), dispersion copolymerization method is adopted to synthesize monodispersed linear polystyrene microballoon seed, take vinylbenzene as monomer, polyvinylpyrrolidone is as stablizer, Diisopropyl azodicarboxylate is initiator, be generate monodispersed polystyrene seed by radical polymerization in reaction medium at ethanolic soln, the particle diameter of seed at 2.5 ~ 3.5 μm, uniform particle sizes;
2), adopt the polystyrene-divinylbenzene-glycidyl methacrylate polystyrene-divinylbenzene-glycidyl methacrylate microballoon of single step seed swelling method synthesis high-crosslinking-degree, get appropriate polystyrene seed, add neck phthalic acid dibutyl ester to activate seed, monomer styrene is added after seed activation, glycidyl methacrylate, cross-linker divinylbenzene, emulsifying agent dodecyl naphthenic acid sodium, stablizer polyvinyl alcohol, initiator benzoyl peroxide, pore-creating agent toluene, stirring makes reaction system fully swelling 12 ~ 24 hours, reheat the carrying out of initiated polymerization, reaction generates monodispersed styrene diethylene benzene copoly mer microballoon, the particle diameter of microballoon is at 5 ~ 7 μm, uniform particle sizes,
3), the Polyamidoamine Dendrimers of different algebraically is synthesized by the Michael reaction of alternate cycles and amidate action, take quadrol as initiated core, methyl alcohol is reaction medium, the first step reaction carries out with methyl acrylate the dendrimer that Michael reaction generated for 0.5 generation, second step reaction by the first step obtain 0.5 generation dendrimer and quadrol generation amidate action generate the dendrimer in 1.0 generations, above two steps are carried out by constantly circulating, can obtain for 1.5 generations, 2.0 generation, 2.5 generation, the Polyamidoamine Dendrimers of the different algebraically such as 3.0 generations,
4), adopt " being grafted to " method to be grafted on polystyrene-divinylbenzene-glycidyl methacrylate microballoon by the Polyamidoamine Dendrimers in integer generation, make microsphere surface modify upper a large amount of amido;
5), adopt active cation reagent 2,3-epoxypropyltrimethylchloride chloride to carry out quaterisation with the amido on the dendrimer be grafted on polystyrene-divinylbenzene-glycidyl methacrylate microballoon, make microballoon quaternary ammonium functionalized;
6), the quaternary ammonium type anion chromatograph packing material with strong retention is obtained, with homogenate method dress post after washing drying.
As improving further, step 4 of the present invention) in, with alcohols or water as solvent, temperature of reaction 50 ~ 80 DEG C, 1 ~ 3 hour reaction times.
As improving further, in step of the present invention (5), the consumption of 2,3-epoxypropyltrimethylchloride chloride is the Polyamidoamine Dendrimers of 8 times and above equivalent, temperature of reaction 60 ~ 80 DEG C, 3 ~ 10 hours reaction times.
As improving further, step 4 of the present invention) in, the macromole be grafted on microballoon is the Polyamidoamine Dendrimers in 1.0 generations, 2.0 generations, 3.0 integer generations in generation.
As improving further, step 2 of the present invention) in stablizer be polyvinylpyrrolidone, initiator is Diisopropyl azodicarboxylate, substitutes stablizer polyvinyl alcohol and initiator benzoyl peroxide.
As improving further, the content of quaternary ammonium root functional group of the present invention can pass through control 2, the ring-opening reaction degree of 3-epoxypropyltrimethylchloride chloride epoxy group(ing) controls, and 2,3-unnecessary epoxypropyltrimethylchloride chlorides can be removed by operations such as washing suction filtrations.
As improving further, the quaternised degree of filler of the present invention can be controlled by the Polyamidoamine Dendrimers of the different algebraically of " being grafted to " mode grafting.
As improving further, step 1 of the present invention) in reaction medium be 95% ethanol.
Advantage of the present invention is as follows:
The present invention is 6 μm with particle diameter, even-grained polystyrene-divinylbenzene-glycidyl methacrylate (PSt-DVB-GMA) is microballoon, and then be grafted on microballoon with Polyamidoamine Dendrimers Grafting to, microsphere surface is made to modify upper a large amount of amido, glycidyl methacrylate (GMA) consumption when preparing microballoon by changing, or by change Grafting to grafting time Polyamidoamine Dendrimers algebraically, microsphere surface can be made to connect the amido of controllable quantity, again by cationic reagent 2, 3-epoxypropyltrimethylchloride chloride (EPTAC) modifies quaternary ammonium cation on amido, by changing cationic reagent 2, the consumption of 3-epoxypropyltrimethylchloride chloride (EPTAC) also can control the quaternization degree of microballoon, thus control filler to the reservation degree of strength of negatively charged ion, the anion chromatographic column of a series of different reserving degree can be obtained.The anion chromatographic filling material prepared can have very strong retention to negatively charged ion, can make F
-, Cl
-effectively be separated with multiple organic acid Deng conventional anion.Packing material size prepared by the method is even, and good rigidly, has obvious selectivity and retention to negatively charged ion, is applicable to the analyzing and testing of different kinds of ions, can be applied to steadily in the long term in ion chromatography detection technique.Because this filler has strong retention, be particularly useful for being separated of multiple organic acid and other negatively charged ion.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph (amplifying 6000 times) of polystyrene-divinylbenzene-glycidyl methacrylate (PSt-DVB-GMA);
Fig. 2 is the chemical structure model of superpolymer (PSt-DVB-GMA)-dendrimer-EPTAC chromatograph packing material;
The color atlas of Fig. 3 conventional anion and organic acid biased sample;
1-F
-(5ppm), 2-acetate moiety (15ppm), 3-Cl
-(5ppm), 4-oxalate (20ppm);
The color atlas of Fig. 4 six kinds of conventional anion;
5-F
-(3ppm)，6-Cl
-(5ppm)，7-NO
3 -(20ppm)，8-Br
-(20ppm)，9-SO
4 2-(10ppm)，10-PO
4 3-(30ppm)；
The chromatograph packing material post of Fig. 5 grafting 2.0 generation dendrimer is to F
-, Cl
-color atlas;
11-F
-(5ppm)，12-Cl
-(1ppm)；
The chromatograph packing material post of Fig. 6 grafting 3.0 generation dendrimer is to F
-, Cl
-color atlas;
13-F
-(3ppm)，14-Cl
-(5ppm)。
Embodiment
The invention discloses a kind of superpolymer polystyrene-divinylbenzene-glycidyl methacrylate-dendrimer-2, the graft type of 3-epoxypropyltrimethylchloride chloride retains by force the preparation method of anion chromatographic filling material, with polystyrene-divinylbenzene-glycidyl methacrylate (PSt-DVB-GMA) for matrix; With quadrol and methyl acrylate for substrate, synthesized the Polyamidoamine Dendrimers (PAMAM) of different algebraically by the Michael addition reaction of alternate cycles and ammonolysis reaction; Dendrimer (PAMAM) is made to be grafted on polystyrene-divinylbenzene-glycidyl methacrylate microballoon (PSt-DVB-GMA) in the mode of Grafting to by controlling reaction conditions; Again with active cation reagent 2,3-epoxypropyltrimethylchloride chloride (EPTAC) carries out quaternized modification to the Polyamidoamine Dendrimers be grafted on PSt-DVB-GMA microballoon, thus obtain the chromatography of ions filler with strong retention, with homogenate method dress post.Concrete implementation step is as follows:
1), dispersion copolymerization method is adopted to synthesize monodispersed linear polystyrene microballoon seed.Take vinylbenzene as monomer, polyvinylpyrrolidone is as stablizer, and Diisopropyl azodicarboxylate is initiator, is generate monodispersed polystyrene seed by radical polymerization in reaction medium at 95% ethanol, the particle diameter of seed at about 3 μm, uniform particle sizes.
2) polystyrene-divinylbenzene-glycidyl methacrylate microballoon (PSt-DVB-GMA) of single step seed swelling method synthesis high-crosslinking-degree, is adopted.Get appropriate polystyrene seed, add neck phthalic acid dibutyl ester to activate seed, monomer styrene, glycidyl methacrylate is added after seed activation, cross-linker divinylbenzene, emulsifying agent dodecyl naphthenic acid sodium, stablizer polyvinyl alcohol or polyvinylpyrrolidone, initiator benzoyl peroxide or formyl Diisopropyl azodicarboxylate, pore-creating agent toluene, stirs and makes reaction system fully swelling, reheat the carrying out of initiated polymerization.Reaction generate monodispersed styrene diethylene benzene copoly mer microballoon, the particle diameter of microballoon at about 6 μm, uniform particle sizes.
3) Polyamidoamine Dendrimers (PAMAM) of different algebraically, is synthesized by the Michael addition reaction of alternate cycles and amidate action.Take quadrol as initiated core, methyl alcohol is reaction medium, and the first step reaction carries out with methyl acrylate the dendrimer that Michael addition reaction generates 0.5G; Second step reacts the dendrimer of 0.5G dendrimer and the quadrol generation amidate action generation 1.0G obtained by the first step; Carrying out above two steps by constantly circulating, the Polyamidoamine Dendrimers of the different algebraically such as 1.5G, 2.0G, 2.5G, 3.0G can be obtained.
4), adopt Grafting to method to be grafted on polystyrene-divinylbenzene-glycidyl methacrylate (PSt-DVB-GMA) microballoon by the Polyamidoamine Dendrimers (PAMAM) in integer generation, make (PSt-DVB-GMA) microsphere surface modify upper a large amount of amido.
5), active cation reagent 2 is adopted, 3-epoxypropyltrimethylchloride chloride (EPTAC) carries out quaterisation with the amido on the dendrimer be grafted on PSt-DVB-GMA microballoon, make microballoon quaternary ammonium functionalized, reaction medium is methyl alcohol, temperature of reaction 60 DEG C.
6), the quaternary ammonium type anion chromatograph packing material with strong retention is obtained, with homogenate method dress post after washing drying.The content of microballoon epoxy group of the present invention is controlled by the amount of the glycidyl methacrylate (GMA) added, the reaction medium of dendrimer synthesis is methyl alcohol, the amido of microsphere surface is the amido on dendrimer side chain, can control by selecting the amine groups content of algebraically to microsphere surface of the dendrimer be grafted on microballoon, what adopt with dendrimer PAMAM grafted polystyrene-Vinylstyrene-glycidyl methacrylate (PSt-DVB-GMA) microballoon is the method for Grafting to, 2 to the reagent of styrene-divinylbenzene-glycidyl methacrylate copolymer microballoon (PSt-DVB-GMA) quaternized employing, 3-epoxypropyltrimethylchloride chloride (EPTAC), reaction medium is methyl alcohol.
Below by specific embodiment, technical scheme of the present invention is further described:
Embodiment 1:
It is as follows for the making processes of graft type anion chromatographic column that Grafting to is grafted to legal system, the steps include:
(1) first synthesize 1.8 μm of single dispersing linear polystyrene seeds by dispersion copolymerization method, then prepare crosslinked monodisperse polystyrene-Vinylstyrene-glycidyl methacrylate (PSt-DVB-GMA) microballoon by seed swelling method.Fig. 1 is the scanning electron microscope (SEM) photograph (amplifying 6000 times) of polystyrene-divinylbenzene-glycidyl methacrylate (PSt-DVB-GMA).
(2) take quadrol as initiated core, methyl alcohol is reaction medium, and the first step reaction is for carry out with methyl acrylate the Polyamidoamine Dendrimers (PAMAM) that Michael addition reaction generates 0.5G; Second step reacts the Polyamidoamine Dendrimers of 0.5G dendrimer and the quadrol generation amidate action generation 1.0G obtained by the first step.Be grafted on polystyrene-divinylbenzene-glycidyl methacrylate (PSt-DVB-GMA) microballoon by the Polyamidoamine Dendrimers Grafting to method of 1.0G, reaction medium is methyl alcohol, and temperature of reaction is 50 DEG C.
(3) active cation reagent 2 is adopted, the amido that 3-epoxypropyltrimethylchloride chloride (EPTAC) and Grafting to are grafted on the dendrimer on microballoon reacts, quaternary ammonium functionalities group in modification, reaction medium methyl alcohol, temperature of reaction 60 DEG C.Fig. 2 is the chemical structure model of this superpolymer (PSt-DVB-GMA)-dendrimer-EPTAC chromatograph packing material.The anion chromatographic filling material with strong retention is obtained, with homogenate method dress post after washing drying.
(4) adopt the sodium hydroxide solution of 10mmol/L as leacheate, flow velocity is 1.00ml/min, adopts Suppressor conductivity detection device to detect conventional anion and organic acid.
(5) this anion chromatographic filling material exchange capacity can by preparing polystyrene-divinylbenzene-glycidyl methacrylate (PSt-DVB-GMA) microballoon time GMA consumption change control; The algebraically that Grafting to method also can be utilized to be grafted to the dendrimer on microballoon controls; Can also be changed by the consumption of cationic reagent EPTAC, reaction times and control quaternised degree, thus prepare the chromatograph packing material of different exchange capacity.
Embodiment 2: chromatographic property is tested
Instrument: SHINEHA CIC-100 ion chromatograph, SHINEHA electrical conductivity detector, SHINEHA SHY-A-III negatively charged ion self-reproduction suppresser
Sample: F
-, Cl
-, acetate moiety, oxalate (being analytical pure)
Leacheate: 10mM/mol NaOH solution
Separator column: homemade filler is loaded in the stainless steel column of 4.6 × 150mm (grafting 1.0 generation dendrimer)
Flow velocity: 1.00ml/min
Fig. 3 is the color atlas of conventional anion and organic acid biased sample
1-F in color atlas
-(5ppm), 2-acetate moiety (15ppm), 3-Cl
-(5ppm), 4-oxalate (20ppm).
Inorganic anion in Fig. 3 can be separated completely with organic acid anions, and retention time is different, illustrates that this chromatograph packing material post has excellent separating effect to organic acid and inorganic anion.
Embodiment 3: chromatographic property is tested
Instrument: SHINEHA CIC-100 ion chromatograph, SHINEHA electrical conductivity detector, SHINEHA SHY-A-III negatively charged ion self-reproduction suppresser
Sample: F
-, Cl
-, NO
3 -, Br
-, PO
4 3-, SO
4 2-(being analytical pure)
Leacheate: 10mM/mol NaOH solution
Separator column: homemade filler is loaded in the stainless steel column of 4.6 × 150mm (grafting 1.0 generation dendrimer)
Flow velocity: 1.00ml/min
Fig. 4 is the color atlas of six kinds of conventional anion
5-F in color atlas
-(3ppm), 6-Cl
-(5ppm), 7-NO
3 -(20ppm), 8-Br
-(20ppm), 9-SO
4 2-(10ppm), 10-PO
4 3-(30ppm).
Six kinds of conventional anion in Fig. 4 can be separated for a full due, and the retention time of each negatively charged ion is different, and illustrating that this chromatograph packing material post has excellent analytical effect to negatively charged ion, is effective anion-exchange column.
Embodiment 4
Instrument: SHINEHA CIC-100 ion chromatograph, SHINEHA electrical conductivity detector, SHINEHA SHY-A-III negatively charged ion self-reproduction suppresser
Sample: F
-, Cl
-(being analytical pure)
Leacheate: 10mM/mol NaOH solution
Separator column: homemade filler is loaded in the stainless steel column of 4.6 × 150mm (grafting 2.0 generation dendrimer)
Flow velocity: 1.00ml/min
Fig. 5 is the color atlas of two kinds of conventional anion, 11-F in color atlas
-(5ppm), 12-Cl
-(1ppm).F in Fig. 5
-, Cl
-can be separated for a full due, the retention time of two kinds of negatively charged ion is different, illustrates that the chromatographic column of grafting 2.0 generation dendrimer is still effective anion chromatographic column.Simultaneously compared with the chromatographic column of grafting 1.0 generation dendrimer, the chromatographic column of grafting 2.0 generation dendrimer is to F
-, Cl
-the retention time of these two kinds of ions becomes for a long time, illustrates that the chromatographic column filler of grafting 2.0 generation dendrimer has stronger retention to negatively charged ion.
Embodiment 5
Instrument: SHINEHA CIC-100 ion chromatograph, SHINEHA electrical conductivity detector, SHINEHA SHY-A-III negatively charged ion self-reproduction suppresser
Sample: F
-, Cl
-(being analytical pure)
Leacheate: 10mM/mol NaOH solution
Separator column: homemade filler is loaded in the stainless steel column of 4.6 × 150mm (grafting 3.0 generation dendrimer)
Flow velocity: 1.00ml/min
Fig. 6 is the color atlas of two kinds of conventional anion, 13-F in color atlas
-(3ppm), 14-Cl
-(5ppm).F in Fig. 6
-, Cl
-can be separated for a full due, the retention time of two kinds of negatively charged ion is different, illustrates that the chromatographic column of grafting 3.0 generation dendrimer is still effective anion chromatographic column.Simultaneously grafting 3.0 generation dendrimer chromatographic column and grafting 1.0 generation/2.0 generations dendrimer chromatographic column compared with, its retention time to these two kinds of ions becomes for a long time, illustrates that the chromatographic column filler of grafting 3.0 generation dendrimer has stronger retention to negatively charged ion.
By the comparison of embodiment 4,5,6, can find, with " being grafted to " method grafting dendrimer on monodisperse polystyrene-Vinylstyrene-glycidyl methacrylate (PSt-DVB-GMA) microballoon, along with the increase of the algebraically of the dendrimer of grafting, chromatograph packing material after quaternized modification can strengthen gradually to the retention of negatively charged ion, and the chromatograph packing material of the dendrimer grafting and modifying of different algebraically all has separation retention to negatively charged ion.Simultaneously by the comparison of embodiment 4,5,6, when can find the dendrimer in grafting 1.0 generation, the separating effect, retention time etc. of this chromatograph packing material are all ideal.
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 (9)
1. superpolymer polystyrene-divinylbenzene-glycidyl methacrylate-dendrimer-2, the graft type of 3-epoxypropyltrimethylchloride chloride retains by force the preparation method of anion chromatographic filling material, it is characterized in that, with polystyrene-divinylbenzene-glycidyl methacrylate for matrix, with quadrol and methyl acrylate for substrate, synthesized the Polyamidoamine Dendrimers of different algebraically by the Michael reaction of alternate cycles and ammonolysis reaction; The Graft Method of " being grafted to " mode of employing, at polystyrene-divinylbenzene-glycidyl glyceryl ester microsphere surface, grafting has the Polyamidoamine Dendrimers of multiple amido end chain; Again with active cation reagent 2,3-epoxypropyltrimethylchloride chloride carries out quaternized modification to the Polyamidoamine Dendrimers be grafted on polystyrene-divinylbenzene-glycidyl methacrylate microballoon, thus obtain the chromatography of ions filler with strong retention, with homogenate method dress post.
2. superpolymer polystyrene-divinylbenzene-glycidyl methacrylate-dendrimer-2 according to claim 1, the graft type of 3-epoxypropyltrimethylchloride chloride retains by force the preparation method of anion chromatographic filling material, it is characterized in that, described concrete preparation process is:
1), dispersion copolymerization method is adopted to synthesize monodispersed linear polystyrene microballoon seed, take vinylbenzene as monomer, polyvinylpyrrolidone is as stablizer, Diisopropyl azodicarboxylate is initiator, be generate monodispersed polystyrene seed by radical polymerization in reaction medium at ethanolic soln, the particle diameter of seed at 2.5 ~ 3.5 μm, uniform particle sizes;
2), adopt the polystyrene-divinylbenzene-glycidyl methacrylate polystyrene-divinylbenzene-glycidyl methacrylate microballoon of single step seed swelling method synthesis high-crosslinking-degree, get appropriate polystyrene seed, add neck phthalic acid dibutyl ester to activate seed, monomer styrene is added after seed activation, glycidyl methacrylate, cross-linker divinylbenzene, emulsifying agent dodecyl naphthenic acid sodium, stablizer polyvinyl alcohol, initiator benzoyl peroxide, pore-creating agent toluene, stirring makes reaction system fully swelling 12 ~ 24 hours, reheat the carrying out of initiated polymerization, reaction generates monodispersed styrene diethylene benzene copoly mer microballoon, the particle diameter of microballoon is at 5 ~ 7 μm, uniform particle sizes,
3), the Polyamidoamine Dendrimers of different algebraically is synthesized by the Michael reaction of alternate cycles and amidate action, take quadrol as initiated core, methyl alcohol is reaction medium, the first step reaction carries out with methyl acrylate the dendrimer that Michael reaction generated for 0.5 generation, second step reaction by the first step obtain 0.5 generation dendrimer and quadrol generation amidate action generate the dendrimer in 1.0 generations, above two steps are carried out by constantly circulating, can obtain for 1.5 generations, 2.0 generation, 2.5 generation, the Polyamidoamine Dendrimers of the different algebraically such as 3.0 generations,
4), adopt " being grafted to " method to be grafted on polystyrene-divinylbenzene-glycidyl methacrylate microballoon by the Polyamidoamine Dendrimers in integer generation, make microsphere surface modify upper a large amount of amido;
5), adopt active cation reagent 2,3-epoxypropyltrimethylchloride chloride to carry out quaterisation with the amido on the dendrimer be grafted on polystyrene-divinylbenzene-glycidyl methacrylate microballoon, make microballoon quaternary ammonium functionalized;
6), the quaternary ammonium type anion chromatograph packing material with strong retention is obtained, with homogenate method dress post after washing drying.
3. superpolymer polystyrene-divinylbenzene-glycidyl methacrylate-dendrimer-2 according to claim 1 and 2, the graft type of 3-epoxypropyltrimethylchloride chloride retains by force the preparation method of anion chromatographic filling material, it is characterized in that, described step 4) in, with alcohols or water as solvent, temperature of reaction 50 ~ 80 DEG C, 1 ~ 3 hour reaction times.
4. superpolymer polystyrene-divinylbenzene-glycidyl methacrylate-dendrimer-2 according to claim 3, the graft type of 3-epoxypropyltrimethylchloride chloride retains by force the preparation method of anion chromatographic filling material, it is characterized in that, in described step (5), 2, the consumption of 3-epoxypropyltrimethylchloride chloride is the Polyamidoamine Dendrimers of 8 times and above equivalent, temperature of reaction 60 ~ 80 DEG C, 3 ~ 10 hours reaction times.
5. superpolymer polystyrene-divinylbenzene-glycidyl methacrylate-dendrimer-2 according to claim 4, the graft type of 3-epoxypropyltrimethylchloride chloride retains by force the preparation method of anion chromatographic filling material, it is characterized in that, described step 4) in, the macromole be grafted on microballoon is the Polyamidoamine Dendrimers in 1.0 generations, 2.0 generations, 3.0 integer generations in generation.
6. the superpolymer polystyrene-divinylbenzene-glycidyl methacrylate-dendrimer-2 according to claim 4 or 5, the graft type of 3-epoxypropyltrimethylchloride chloride retains by force the preparation method of anion chromatographic filling material, it is characterized in that, described step 2) in stablizer be polyvinylpyrrolidone, initiator is Diisopropyl azodicarboxylate, substitutes stablizer polyvinyl alcohol and initiator benzoyl peroxide.
7. superpolymer polystyrene-divinylbenzene-glycidyl methacrylate-dendrimer-2 according to claim 6, the graft type of 3-epoxypropyltrimethylchloride chloride retains by force the preparation method of anion chromatographic filling material, it is characterized in that, the content of described quaternary ammonium root functional group can pass through control 2, the ring-opening reaction degree of 3-epoxypropyltrimethylchloride chloride epoxy group(ing) controls, 2,3-unnecessary epoxypropyltrimethylchloride chlorides can be removed by operations such as washing suction filtrations.
8. superpolymer polystyrene-divinylbenzene-glycidyl methacrylate-dendrimer-2 according to claim 7, the graft type of 3-epoxypropyltrimethylchloride chloride retains by force the preparation method of anion chromatographic filling material, it is characterized in that, the quaternised degree of filler can be controlled by the Polyamidoamine Dendrimers of the different algebraically of " being grafted to " mode grafting.
9. the superpolymer polystyrene-divinylbenzene-glycidyl methacrylate-dendrimer-2 according to claim 7 or 8, the graft type of 3-epoxypropyltrimethylchloride chloride retains by force the preparation method of anion chromatographic filling material, it is characterized in that, described step 1) in reaction medium be 95% ethanol.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510351526.9A CN104945637B (en) | 2015-06-24 | 2015-06-24 | A kind of graft type retains by force the preparation method of anion chromatographic filling material |
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|---|---|---|---|
| CN201510351526.9A CN104945637B (en) | 2015-06-24 | 2015-06-24 | A kind of graft type retains by force the preparation method of anion chromatographic filling material |
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| CN104945637B CN104945637B (en) | 2018-05-11 |
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Cited By (11)
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| CN105396628A (en) * | 2015-12-06 | 2016-03-16 | 杭州飞山浩科技有限公司 | Preparation method of polyethylene polyamine graft-modified polystyrene-divinyl benzene ion chromatographic packing |
| 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 |
| CN107255683A (en) * | 2017-07-05 | 2017-10-17 | 中国人民解放军63605部队 | A kind of hydrazine propellant analysis filling column preparation method |
| 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 |
| CN108636379A (en) * | 2018-05-14 | 2018-10-12 | 华南理工大学 | A kind of positively charged polystyrene microsphere and its preparation method and application |
| CN109248715A (en) * | 2018-09-26 | 2019-01-22 | 安徽皖仪科技股份有限公司 | Anion exchange resin and its preparation method and application |
| CN109254086A (en) * | 2017-06-20 | 2019-01-22 | 海南先声药业有限公司 | A kind of HPLC detection method of lauryl sodium sulfate in cefaclor dry suspensoid sample |
| CN109608585A (en) * | 2018-12-20 | 2019-04-12 | 华东理工大学 | Surface grafting polymerization type anion chromatographic stationary phase and preparation method thereof and ion chromatographic column |
| CN110327990A (en) * | 2019-07-30 | 2019-10-15 | 王金平 | A kind of preparation method of latex agglomeration type anion chromatographic column packing |
| CN111389052A (en) * | 2020-03-13 | 2020-07-10 | 中谱科技(福州)有限公司 | Preparation and application of polyamide high performance liquid chromatography column |
| CN115414921A (en) * | 2022-08-30 | 2022-12-02 | 赛分科技扬州有限公司 | Surface modification method of ion exchange filler |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105396628A (en) * | 2015-12-06 | 2016-03-16 | 杭州飞山浩科技有限公司 | Preparation method of polyethylene polyamine graft-modified polystyrene-divinyl benzene ion chromatographic packing |
| 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 |
| CN109254086A (en) * | 2017-06-20 | 2019-01-22 | 海南先声药业有限公司 | A kind of HPLC detection method of lauryl sodium sulfate in cefaclor dry suspensoid sample |
| CN107255683A (en) * | 2017-07-05 | 2017-10-17 | 中国人民解放军63605部队 | A kind of hydrazine propellant analysis filling column preparation method |
| 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 |
| CN108636379A (en) * | 2018-05-14 | 2018-10-12 | 华南理工大学 | A kind of positively charged polystyrene microsphere and its preparation method and application |
| CN109248715A (en) * | 2018-09-26 | 2019-01-22 | 安徽皖仪科技股份有限公司 | Anion exchange resin and its preparation method and application |
| CN109608585A (en) * | 2018-12-20 | 2019-04-12 | 华东理工大学 | Surface grafting polymerization type anion chromatographic stationary phase and preparation method thereof and ion chromatographic column |
| CN110327990A (en) * | 2019-07-30 | 2019-10-15 | 王金平 | A kind of preparation method of latex agglomeration type anion chromatographic column packing |
| CN111389052A (en) * | 2020-03-13 | 2020-07-10 | 中谱科技(福州)有限公司 | Preparation and application of polyamide high performance liquid chromatography column |
| CN115414921A (en) * | 2022-08-30 | 2022-12-02 | 赛分科技扬州有限公司 | Surface modification method of ion exchange filler |
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