CN105396628B - The preparation method of polyethylene polyamine graft modification polystyrene divinylbenzene chromatography of ions filler - Google Patents
The preparation method of polyethylene polyamine graft modification polystyrene divinylbenzene chromatography of ions filler Download PDFInfo
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- CN105396628B CN105396628B CN201510890879.6A CN201510890879A CN105396628B CN 105396628 B CN105396628 B CN 105396628B CN 201510890879 A CN201510890879 A CN 201510890879A CN 105396628 B CN105396628 B CN 105396628B
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Abstract
The invention discloses one kind 2, the preparation method of the polyethylene polyamine graft modification polystyrene divinylbenzene chromatography of ions filler of 3 epoxypropyltrimethylchloride chlorides modification is using polystyrene divinylbenzene microballoon as carrier matrix, polystyrene divinylbenzene microballoon is modified by GMA, obtain the MPS divinylbenzene microspheres with epoxide group, the polyethylene polyamine quasi-molecule such as diethylenetriamine or triethylene tetramine or TEPA is grafted on modified polystyrene divinylbenzene microballoon again, modification microballoon after grafting is with 2, 3 epoxy third class trimethyl ammonium chlorides carry out functional modification.The present invention uses GMA MPS divinylbenzene microspheres, make microsphere supported there is epoxide group, the polyamines polyene class such as diethylenetriamine or triethylene tetramine is grafted on modified microballoon again, makes the upper substantial amounts of amido of microsphere surface modification.
Description
Technical field
The present invention relates to a kind of preparation method of chromatograph packing material, is one kind 2,3- epoxy chlorine specifically
Change the preparation method of the polyethylene polyamine graft modification polystyrene-divinylbenzene chromatography of ions filler of ammonium modification.
Background technology
Chromatography of ions (IC) is an important branch of high performance liquid chromatography (HPLC), is application in chromatography field
One of branch most wide, with fastest developing speed, it is the preferred gimmick of all kinds of zwitterion analyses.Chromatography of ions has superior sensitive
Degree, selectivity, especially in the biology point such as analytic routines anions and canons, organic acid, fatty amine, aromatic amine and carbohydrate, amino acid
Son plays extremely important effect.Chromatography of ions is initially applied to the analysis of underwater trace anions and canons in environmental monitoring, with
The ripe raising with detection level of continuous development of ion chromatographic separation technology, chromatography of ions is also widely used in electric power at present
With energy industry, electronics industry, food beverage industry, pharmaceutical industry, chemical industry and life science.
The most general separate mode of chromatography of ions is ion-exchange, and stationary phase is ion exchange resin filler.Stationary phase
It is made up of insoluble medium carrier and functional group.Medium carrier determines size and the distribution of filler, and filler particles resist
Compressive Strength, pore radiuses and distribution, rigidity and stability of filling-material structure etc., the structural property of matrix also determines chemical modification
The implementation of method.The medium carrier of ion exchange resin filler includes silica gel and the class of high molecular polymer two.Functional group and base
The combination of matter carrier includes Covalent bonding together, such as carries out direct ion modification on surface；Surface agglomeration refers to functional base
The individual layer latex of group is attached to matrix microspheres surface ion bond with electrostatic force and closed；Surface-grafted type is to pass through compound
Chemical reaction is bonded with matrix, is then modified by the molecule in grafting.
The anion-exchange chromatography filler of silica gel type is that have silica gel particle outer layer to apply the dodecane that last layer contains quaternary amine base
Methacrylate polymer (relative molecular weight 500).In general ion exchange capacity is 0.012mmol/g, admissible
PH scopes are 4~9, not strong alkali-acid resistance.Macromolecule copolymer resin is resistant to very wide H scopes (pH0~14), can use strong acid or
Highly basic makees leacheate, and more general has polystyrene-divinylbenzene resin (PSt-DVB), vinyl xylene, ethyl vinyl benzene-divinyl
The matrix such as base benzene copolymer (EVB-DVB), polymethacrylates and polyethylene polymer, wherein PSt-DVB are important the moon
Ion exchange stationary phase host material.PSt-DVB type ion exchange resin is to be suspended to gather by styrene and divinylbenzene monomers
Conjunction obtains, and has network structure.Cross-linkage of resin, divinylbenzene can be controlled according to the content difference of divinylbenzene
Content is higher, and the degree of cross linking is big, and forming macroporous ion-exchange resin has rigid structure, there is certain hole inside resin.In medium carrier
Functional group is introduced on microballoon, the functional group of anion exchange resin is mainly quaternary ammonium group.
The content of the invention
The present invention makes improvements in view of the deficiencies of the prior art, there is provided one kind 2,3- epoxypropyl trimethylammonium chlorides
The preparation method of the polyethylene polyamine graft modification polystyrene-divinylbenzene chromatography of ions filler of ammonium modification, by 2,3- rings
The diethylenetriamine of oxygen hydroxypropyltrimonium chloride modification, the polyethylene polyamine class such as triethylene tetramine are grafted in a manner of " being grafted to "
The preparation method of the anion chromatographic filling material of modified polystyrene-divinylbenzene, and active cation reagent 2,3- rings
The polyethylene polyamine classes such as oxygen third class trimethyl ammonium chloride (EPTAC), diethylenetriamine, triethylene tetramine are prepared in chromatograph packing material and closed
Application process in.
The present invention is achieved by the following technical solutions：
The invention discloses a kind of polyethylene polyamine graft modification polyphenyl of 2,3- epoxypropyltrimethylchloride chlorides modification
The preparation method of ethene-divinyl benzene ion chromatograph packing material, using polystyrene-divinylbenzene microspheres as carrier matrix, lead to
Cross GMA to be modified polystyrene-divinylbenzene microspheres, obtain that there is changing for epoxide group
Property polystyrene-divinylbenzene microspheres, then by the polyethylene polyamine such as diethylenetriamine or triethylene tetramine or TEPA
Quasi-molecule is grafted on modified polystyrene-divinylbenzene microspheres, and the modification microballoon after grafting is with 2,3- epoxies third class three
Ammonio methacrylate (EPTAC) carries out functional modification, and the quaternary ammonium type anion that finally giving has retention to anion is handed over
Chromatograph packing material is changed, with homogenate method dress post.
As a further improvement, specific preparation process of the present invention is：
1) monodispersed linear polystyrene microballoon seed, using styrene as monomer, poly- second, are synthesized using dispersion copolymerization method
For alkene pyrrolidone as stabilizer, azodiisobutyronitrile is initiator, is drawn in ethanol solution is reaction medium by free radical
Send out polymerisation and generate monodispersed polystyrene seed；
2) the polystyrene-divinylbenzene medium carrier microballoon of high-crosslinking-degree, is synthesized using single step seed swelling method.Take
Appropriate polystyrene seed, add neck dibatyl phithalate seed is activated, after seed activation add styrene monomer,
Divinylbenzene monomers, emulsifying agent dodecyl sodium sulfate, stabilizer polyvinyl alcohol, initiator benzoyl peroxide, pore-foaming agent
Toluene, stirring make reaction system fully be swelled 12 to 24 hours, heat initiated polymerization, reaction generation monodisperse polystyrene
Alkene-divinylbenzene microspheres；
3), polystyrene-divinylbenzene microspheres are modified using GMA；
4) hyperbranched modification, is carried out to modified microballoon using the polyethylene polyamine such as diethylenetriamine or triethylene tetramine class,
Make microballoon that there is amido；
5) microballoon of step 4) processing, is passed through using 2,3- epoxypropyltrimethylchloride chlorides (EPTAC) functional modification,
Finally giving has the quaternary ammonium type anion exchange resin of retention to anion；
6), wash dried chromatograph packing material and fill post with homogenate method.
As a further improvement, the particle diameter of seed seed is at 2.5~3.5 μm in step 1) of the present invention, particle diameter
It is evenly distributed, reaction medium is 95% ethanol.
As a further improvement, for the particle diameter of microballoon at 5~7 μm, particle diameter distribution is uniform in step 2) of the present invention,
Stabilizer is polyvinylpyrrolidone, and initiator is azodiisobutyronitrile.
As a further improvement, in step 4) of the present invention, reaction medium is Isosorbide-5-Nitrae-dioxane：Toluene mixes
Solution, 80~90 DEG C of reaction temperature, 10~12 hours reaction time.
As a further improvement, in described step 5) of the present invention, 2,3- epoxypropyltrimethylchloride chlorides
Dosage be the polyethylene polyamine quasi-molecule such as 8 times and the diethylenetriamine of above equivalent or triethylene tetramine, reaction temperature 50~
60 DEG C, 2~4 hours reaction time.
As a further improvement, in step 4) of the present invention, the polyethylene polyamine class that is grafted on modified microballoon
Molecule can be ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA, pentaethylene hexamine, the amine of six ethene seven and spread out
Biological dipropylenetriamine molecule.
As a further improvement, the content of quaternary ammonium root functional group of the present invention can be by controlling 2,3- epoxies
The ring-opening reaction degree of hydroxypropyltrimonium chloride epoxy radicals controls, and unnecessary 2,3- epoxypropyltrimethylchloride chlorides pass through
The operations such as washing suction filtration can remove.
As a further improvement, the quaternized degree of anion-exchange chromatography filler of the present invention can be by connecing
The chain length of the polyethylene polyamine quasi-molecule of branch is controlled, and chain length is longer, and institute's amino-contained is more, and final quaternized degree will
It is higher.Chain length is followed successively by diethylenetriamine, triethylene tetramine, TEPA, pentaethylene hexamine, six ethene seven by short and length
Amine, the amine of seven ethene eight.The invention discloses a kind of the poly- of the polyethylene polyamine class graft modification such as diethylenetriamine, triethylene tetramine
Styrene-divinylbenzene microballoon, then with micro- after the grafting of 2,3- epoxypropyltrimethylchloride chlorides (EPTAC) functional modification
Ball, so as to synthesize the preparation method of the quaternary ammonium type anion chromatograph packing material to anion with strong retention.With polystyrene-
Divinylbenzene microspheres are carrier matrix, and polystyrene-divinylbenzene microspheres are entered by GMA
Row is modified, and obtains the MPS-divinylbenzene microspheres with epoxide group, then by diethylenetriamine or triethylene four
The polyethylene polyamine quasi-molecule such as amine or TEPA is grafted on modified polystyrene-divinylbenzene microspheres, after grafting
Modification microballoon with 2,3- epoxy third class trimethyl ammonium chlorides (EPTAC) carry out functional modification, finally give to anion have
The quaternary ammonium type anion exchange chromatography filler for effect of withing a hook at the end, with homogenate method dress post.
As a further improvement, it is of the present invention to concretely comprise the following steps：
1) monodispersed linear polystyrene microballoon seed, using styrene as monomer, poly- second, are synthesized using dispersion copolymerization method
For alkene pyrrolidone as stabilizer, azodiisobutyronitrile is initiator, and ethanol solution is reaction medium, is triggered by free radical
Polymerisation generates monodispersed polystyrene seed, and for the particle diameter of seed at 2.5~3.5 μm, particle diameter distribution is uniform；
2) the polystyrene-divinylbenzene medium carrier microballoon of high-crosslinking-degree, is synthesized using single step seed swelling method.Take
Appropriate polystyrene seed, add neck dibatyl phithalate seed is activated, after seed activation add styrene monomer,
Divinylbenzene monomers, emulsifying agent dodecyl sodium sulfate, stabilizer polyvinyl alcohol, initiator benzoyl peroxide, pore-foaming agent
Toluene, stirring make reaction system fully be swelled 12 to 24 hours, heat initiated polymerization, reaction generation monodisperse polystyrene
Alkene-divinylbenzene microspheres, for the particle diameter of microballoon at 5~7 μm, particle diameter distribution is uniform；
3), polystyrene-divinylbenzene microspheres are modified using GMA；
4) hyperbranched modification, is carried out to modified microballoon using the polyethylene polyamine such as diethylenetriamine or triethylene tetramine class,
Make microballoon that there is amido；
5), using 2,3- epoxypropyltrimethylchloride chlorides (EPTAC) functional modification pass through 4) processing microballoon, finally
Obtain the quaternary ammonium type anion exchange resin to anion with retention.
6), wash dried chromatograph packing material and fill post with homogenate method.
As a further improvement, reaction medium is 95% ethanol in step 1) of the present invention.
As a further improvement, the stabilizer in step 2) of the present invention is polyvinylpyrrolidone, initiator
For azodiisobutyronitrile.
As a further improvement, in step 4) of the present invention, with Isosorbide-5-Nitrae-dioxane：Toluene (4:1) as molten
Agent, 80~90 DEG C of reaction temperature, 10~12 hours reaction time.
As a further improvement, in step 5) of the present invention, the dosage of 2,3- epoxypropyltrimethylchloride chlorides
For the polyethylene polyamine class such as 8 times and the diethylenetriamine of above equivalent or triethylene tetramine, 50~60 DEG C of reaction temperature, during reaction
Between 2~4 hours.
As a further improvement, polyethylene polyamine class of the present invention includes ethylenediamine, diethylenetriamine, triethylene
Tetramine, TEPA, pentaethylene hexamine, the amine of six ethene seven and derivative dipropylenetriamine etc. connect to modified microballoon
Branch.
As a further improvement, the content of quaternary ammonium root functional group of the present invention can be by controlling 2,3- epoxies
The ring-opening reaction degree of hydroxypropyltrimonium chloride epoxy radicals controls, and unnecessary 2,3- epoxypropyltrimethylchloride chlorides pass through
The operations such as washing suction filtration can remove.
Advantages of the present invention is as follows：
The present invention uses GMA MPS-divinylbenzene microspheres, makes microsphere supported tool
There is epoxide group, then the polyamines polyene class such as diethylenetriamine or triethylene tetramine is grafted on modified microballoon, make microballoon
Substantial amounts of amido in surface modification.Polystyrene divinyl can be changed by the dosage for changing GMA
Base benzene modification degree, the i.e. content of epoxy radicals.By selecting different polyamines polyene quasi-molecules, such as diethylenetriamine, triethylene
Tetramine, TEPA etc. can change the amido amount in microsphere surface grafting.Pass through 2,3- epoxypropyl trimethylammonium chlorides again
Ammonium (EPTAC) carries out quaternized functionalized modification to the amido of microsphere surface.By being grafted the polyethylene polyamine of different chain length, to season
Ammonium degree is controlled change, so as to which the anion-exchange chromatography filler to anion with different retentions be made.Such as
Chromatograph packing material using diethylenetriamine and triethylene tetramine as grafting molecules has stronger and different retention to anion,
A variety of organic acids such as general inorganic anion and lactic acid, oxalic acid can be efficiently separated.
Brief description of the drawings
Fig. 1 is diethylenetriamine-MPS-divinylbenzene -- the chemical structure model of EPTAC chromatograph packing materials；
Fig. 2 is triethylene tetramine-MPS-divinylbenzene -- the chemical structure model of EPTAC chromatograph packing materials；
Fig. 3 is TEPA-MPS-divinylbenzene -- the chemical structure model of EPTAC chromatograph packing materials；
Fig. 4 diethylenetriamines-MPS-divinylbenzene -- EPTAC chromatograph packing materials are to six kinds of conventional anions
Chromatogram；1-F-(1ppm), 2-Cl-(2ppm), 3-NO2 -(5ppm), 4-Br-(5ppm), 5-SO4 2-(6ppm), 6-NO3 -
(5ppm)；
Fig. 5 triethylene tetramines-MPS-divinylbenzene -- EPTAC chromatograph packing materials are to conventional anion and have
The chromatogram of the biased sample of machine acid；
1-F-(1ppm), 5-SO4 2-(6ppm), 7- acetates (15ppm), 8- propionates (15ppm), 9- bromates
(5ppm), 10- chloroacetic acid roots, 11- oxalates (20ppm).
Embodiment
The invention discloses a kind of polystyrene-divinylbenzene matrix microspheres of modification to be grafted more second such as diethylenetriamine
The more amine molecules of alkene, then the method that anion chromatographic filling material is prepared with 2,3- epoxypropyltrimethylchloride chloride rhetorical functions.
Using polystyrene-divinylbenzene as matrix microspheres, microballoon is carried out with GMA epoxy-modified；With
The polyethylene polyamine quasi-molecule graft modification polystyrene-divinyl base such as diethylenetriamine, triethylene tetramine or TEPA
Benzene microballoon；Quaternary ammonium functional group modification is carried out to the microballoon after grafting with 2,3- epoxypropyltrimethylchloride chlorides, so as to obtain pair
Anion has the anion-exchange chromatography filler of retention, with homogenate method dress post.Specific implementation step is as follows：
1) monodispersed linear polystyrene microballoon seed, is synthesized using dispersion copolymerization method.Using styrene as monomer, poly- second
For alkene pyrrolidone as stabilizer, azodiisobutyronitrile is initiator, is drawn in 95% ethanol is reaction medium by free radical
Send out polymerisation and generate monodispersed polystyrene seed, the particle diameter of seed is at 3 μm or so, uniform particle sizes.
2) the polystyrene-divinylbenzene medium carrier microballoon of high-crosslinking-degree, is synthesized using single step seed swelling method.Take
Appropriate polystyrene seed, add neck dibatyl phithalate seed is activated, after seed activation add styrene monomer,
Divinylbenzene monomers, emulsifying agent dodecyl sodium sulfate, stabilizer polyvinyl alcohol, initiator benzoyl peroxide, pore-foaming agent
Toluene, stirring make reaction system fully be swelled, and reheat initiated polymerization, reaction generation monodisperse polystyrene-divinyl
Base benzene microballoon, for the particle diameter of microballoon at 5~7 μm, particle diameter distribution is uniform；
3), polystyrene-divinylbenzene microspheres are modified using GMA, have microballoon
There are a large amount of epoxy radicals；
4), modified microballoon is carried out using the polyethylene polyamine such as diethylenetriamine or triethylene tetramine or TEPA class
Hyperbranched modification, makes microballoon have amido；
5), using 2,3- epoxypropyltrimethylchloride chlorides (EPTAC) functional modification pass through 4) processing microballoon, finally
Obtain the quaternary ammonium type anion exchange resin to anion with retention；
6), wash dried chromatograph packing material and fill post with homogenate method.
The content of MPS of the present invention-divinylbenzene microspheres epoxy radicals can pass through the methacrylic acid of addition
The amount of ethylene oxidic ester (GMA) is controlled, and the reaction medium of grafting polyethylene polyamine quasi-molecule is Isosorbide-5-Nitrae-dioxane：Toluene
(4:1) mixed solution, the amido of microsphere surface is the amido on polyethylene polyamine, and the quaternized method of microsphere surface amido is adopted
Reagent is 2,3- epoxypropyltrimethylchloride chlorides (EPTAC).
Technical scheme is further described below by specific embodiment：
Embodiment 1
The diethylenetriamine graft modification polystyrene-divinylbenzene of 2,3- epoxypropyltrimethylchloride chlorides modification
The manufacturing process of ion chromatographic column is as follows, and its step is：
(1) first pass through dispersion copolymerization method and synthesize 1.8 μm of single dispersing linear polystyrene seeds, then pass through seed swelling method
Monodisperse polystyrene-divinylbenzene (PSt-DVB) microballoon of crosslinking is prepared.With GMA pair
Polystyrene-divinylbenzene microspheres are modified, and microballoon is had a large amount of epoxy radicals；
(2) hyperbranched modification is carried out to modified microballoon using diethylenetriamine, makes microballoon that there is amido, reaction medium 1,
4- dioxane：Toluene (volume ratio 4:1), reaction temperature is 80 DEG C.
(3) it is micro- to being grafted to modification using active cation reagent 2,3- epoxypropyltrimethylchloride chlorides (EPTAC)
Amido on ball carries out quaternized functional modification, 50 DEG C of reaction temperature.Fig. 1 is diethylenetriamine-MPS-diethyl
Alkenyl benzene -- the chemical structure model of EPTAC chromatograph packing materials.Washing obtains having the anion chromatographic of retention to fill out after drying
Material, with homogenate method dress post.
(4) using 10mmol/L sodium hydroxide solution as leacheate, flow velocity 1.00ml/min, using suppression conductance
Detector detects to conventional anion and organic acid.
Fig. 1 is diethylenetriamine-MPS-divinylbenzene -- the chemical structure model of EPTAC chromatograph packing materials.
Embodiment 2
The triethylene tetramine graft modification polystyrene-divinylbenzene of 2,3- epoxypropyltrimethylchloride chlorides modification
The manufacturing process of ion chromatographic column is as follows, and its step is：
(1) first pass through dispersion copolymerization method and synthesize 1.8 μm of single dispersing linear polystyrene seeds, then pass through seed swelling method
Monodisperse polystyrene-divinylbenzene (PSt-DVB) microballoon of crosslinking is prepared.With GMA pair
Polystyrene-divinylbenzene microspheres are modified, and microballoon is had a large amount of epoxy radicals；
(2) hyperbranched modification is carried out to modified microballoon using triethylene tetramine, makes microballoon that there is amido, reaction medium 1,
4- dioxane：Toluene (volume ratio 4:1), reaction temperature is 85 DEG C.
(3) it is micro- to being grafted to modification using active cation reagent 2,3- epoxypropyltrimethylchloride chlorides (EPTAC)
Amido on ball carries out quaternized functional modification, 55 DEG C of reaction temperature.Fig. 2 is triethylene tetramine-MPS-diethyl
Alkenyl benzene -- the chemical structure model of EPTAC chromatograph packing materials.Washing obtains having the anion chromatographic of retention to fill out after drying
Material, with homogenate method dress post.
(4) using 10mmol/L sodium hydroxide solution as leacheate, flow velocity 1.00ml/min, using suppression conductance
Detector detects to conventional anion and organic acid.
Fig. 2 is triethylene tetramine-MPS-divinylbenzene -- the chemical structure model of EPTAC chromatograph packing materials.
Embodiment 3
The TEPA graft modification polystyrene-divinylbenzene of 2,3- epoxypropyltrimethylchloride chlorides modification
The manufacturing process of ion chromatographic column is as follows, and its step is：
(1) first pass through dispersion copolymerization method and synthesize 1.8 μm of single dispersing linear polystyrene seeds, then pass through seed swelling method
Monodisperse polystyrene-divinylbenzene (PSt-DVB) microballoon of crosslinking is prepared.With GMA pair
Polystyrene-divinylbenzene microspheres are modified, and microballoon is had a large amount of epoxy radicals；
(2) hyperbranched modification is carried out to modified microballoon using TEPA, makes microballoon that there is amido, reaction medium 1,
4- dioxane：Toluene (volume ratio 4:1), reaction temperature is 90 DEG C.
(3) it is micro- to being grafted to modification using active cation reagent 2,3- epoxypropyltrimethylchloride chlorides (EPTAC)
Amido on ball carries out quaternized functional modification, 60 DEG C of reaction temperature.Fig. 3 is TEPA-MPS-diethyl
Alkenyl benzene -- the chemical structure model of EPTAC chromatograph packing materials.Washing obtains having the anion chromatographic of retention to fill out after drying
Material, with homogenate method dress post.
(4) using 10mmol/L sodium hydroxide solution as leacheate, flow velocity 1.00ml/min, using suppression conductance
Detector detects to conventional anion and organic acid.
Fig. 3 is TEPA-MPS-divinylbenzene -- the chemical structure model of EPTAC chromatograph packing materials.
Embodiment 4
Diethylenetriamine-MPS-divinylbenzene -- EPTAC column performances are tested
Instrument：Dionex ICS-2000 ion chromatographs are equipped with DS6 conductance cells, ASRS-4mm anion suppressors, EG50
Elute liquid generator, self-control ion chromatographic column
Sample：F-, Cl-, NO2 -, Br-, SO4 2-, NO3 -(being that analysis is pure)
Leacheate：10mM/mol KOH solutions
Splitter：Homemade filler is filled in 4.6 × 150mm stainless steel columns
Flow velocity：1.00ml/min
Fig. 4 is the chromatogram of six kinds of conventional anion samples
1-F in chromatogram-(1ppm), 2-Cl-(2ppm), 3-NO2 -(5ppm), 4-Br-(5ppm), 5-SO4 2-(6ppm), 6-
NO3 -(5ppm)。
Six kinds of conventional anions in Fig. 4 can separate for a full due, and the retention time of each anion is different, says
The bright chromatograph packing material post has excellent analytical effect to anion, is effective anion-exchange column.
Embodiment 5
Triethylene tetramine-MPS-divinylbenzene -- EPTAC column performances are tested
Instrument：Dionex ICS-2000 ion chromatographs are equipped with DS6 conductance cells, ASRS-4mm anion suppressors, EG50
Elute liquid generator, self-control ion chromatographic column
Sample：F-, SO4 2, acetate, propionate, bromate, chloroacetic acid root, oxalate
Leacheate：15mM/mol KOH solutions
Splitter：Homemade filler is filled in 4.6 × 150mm stainless steel columns
Flow velocity：1.00ml/min
Fig. 5 is the chromatogram of general inorganic anion and organic acid biased sample
1-F in chromatogram-(1ppm), 5-SO4 2-(6ppm), 7- acetates (15ppm), 8- propionates (15ppm), 9- bromines
Acid group (5ppm), 10- chloroacetic acid roots, 11- oxalates (20ppm).
Inorganic anion and organic acid anions in Fig. 5 can be kept completely separate, and retention time is different, illustrate the chromatogram
Filled column has excellent separating effect to organic acid and inorganic anion.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair
It is bright.The invention is not restricted to embodiment here, those skilled in the art change according to the announcement of the present invention for what the present invention made
Entering and change all should be within protection scope of the present invention.
Claims (9)
- A kind of 1. polyethylene polyamine graft modification polystyrene-divinylbenzene of 2,3- epoxypropyltrimethylchloride chlorides modification The preparation method of chromatography of ions filler, it is characterized in that, using polystyrene-divinylbenzene microspheres as carrier matrix, pass through methyl Glycidyl acrylate is modified to polystyrene-divinylbenzene microspheres, obtains the modified polyphenyl with epoxide group Ethene-divinylbenzene microspheres, then polyethylene polyamine molecule is grafted on modified polystyrene-divinylbenzene microspheres, Modification microballoon after grafting carries out functional modification with 2,3- epoxypropyltrimethylchloride chlorides (EPTAC), finally gives to the moon Ion has the quaternary ammonium type anion exchange chromatography filler of retention, with homogenate method dress post.
- 2. the polyethylene polyamine graft modification polyphenyl of 2,3- epoxypropyltrimethylchloride chlorides modification according to claim 1 The preparation method of ethene-divinyl benzene ion chromatograph packing material, it is characterized in that, specific preparation process is：1) monodispersed linear polystyrene microballoon seed, using styrene as monomer, polyethylene pyrrole, are synthesized using dispersion copolymerization method For pyrrolidone as stabilizer, azodiisobutyronitrile is initiator, is triggered in ethanol solution is reaction medium by free radical and gathered Close reaction and generate monodispersed polystyrene seed；2) the polystyrene-divinylbenzene medium carrier microballoon of high-crosslinking-degree, is synthesized using single step seed swelling method, is taken appropriate Polystyrene seed, add dibutyl phthalate and seed is activated, styrene monomer, diethyl are added after seed activation Alkenyl benzene monomer, emulsifying agent dodecyl sodium sulfate, stabilizer polyvinyl alcohol, initiator benzoyl peroxide, pore-foaming agent toluene, Stirring makes reaction system fully be swelled 12 to 24 hours, heats initiated polymerization, reaction generation monodisperse polystyrene-diethyl Alkenyl benzene microballoon；3), polystyrene-divinylbenzene microspheres are modified using GMA；4) hyperbranched modification, is carried out to modified microballoon using polyethylene polyamine, makes microballoon that there is amido；5) microballoon of step 4) processing, is passed through using 2,3- epoxypropyltrimethylchloride chlorides (EPTAC) functional modification, finally Obtain the quaternary ammonium type anion exchange resin to anion with retention；6), wash dried chromatograph packing material and fill post with homogenate method.
- 3. the polyethylene polyamine graft modification polyphenyl of 2,3- epoxypropyltrimethylchloride chlorides modification according to claim 2 The preparation method of ethene-divinyl benzene ion chromatograph packing material, it is characterized in that, the particle diameter of seed is 2.5 in described step 1) ~3.5 μm, particle diameter distribution is uniform, and reaction medium is ethanol.
- 4. the polyethylene polyamine graft modification polyphenyl of 2,3- epoxypropyltrimethylchloride chlorides modification according to claim 2 The preparation method of ethene-divinyl benzene ion chromatograph packing material, it is characterized in that, the particle diameter of microballoon is 5~7 in described step 2) μm, particle diameter distribution is uniform, and stabilizer is polyvinylpyrrolidone, and initiator is azodiisobutyronitrile.
- 5. the polyethylene polyamine graft modification of the 2,3- epoxypropyltrimethylchloride chlorides modification according to claim 2 or 4 The preparation method of polystyrene-divinylbenzene chromatography of ions filler, it is characterized in that, in described step 4), reaction medium is 1,4- dioxane：Toluene mixed solution, 80~90 DEG C of reaction temperature, 10~12 hours reaction time.
- 6. the polyethylene polyamine graft modification polyphenyl of 2,3- epoxypropyltrimethylchloride chlorides modification according to claim 5 The preparation method of ethene-divinyl benzene ion chromatograph packing material, it is characterized in that, in described step 5), 2,3- glycidyl three The dosage of ammonio methacrylate is the polyethylene polyamine molecule of 8 times and above equivalent, 50~60 DEG C of reaction temperature, the reaction time 2~4 Hour.
- 7. the polyethylene polyamine graft modification polyphenyl of 2,3- epoxypropyltrimethylchloride chlorides modification according to claim 5 The preparation method of ethene-divinyl benzene ion chromatograph packing material, it is characterized in that, in described step 4), it is grafted to modified microballoon On polyethylene polyamine molecule be ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA, pentaethylene hexamine, six ethene Seven amine and derivative dipropylenetriamine molecule.
- 8. the polyethylene polyamine of the 2,3- epoxypropyltrimethylchloride chlorides modification according to claim 1 or 2 or 4 or 6 or 7 The preparation method of graft modification polystyrene-divinylbenzene chromatography of ions filler, it is characterized in that, described quaternary ammonium root functional group The content of group can be controlled by controlling the ring-opening reaction degree of 2,3- epoxypropyltrimethylchloride chloride epoxy radicals, unnecessary 2,3- epoxypropyltrimethylchloride chlorides can be removed by washing suction filtration operation.
- 9. the polyethylene polyamine graft modification polyphenyl of 2,3- epoxypropyltrimethylchloride chlorides modification according to claim 8 The preparation method of ethene-divinyl benzene ion chromatograph packing material, it is characterized in that, described anion-exchange chromatography filler is quaternized Degree can be controlled by the chain length of the polyethylene polyamine molecule of grafting, chain length is longer, and institute's amino-contained is more, final season The degree of ammonium will be higher, and chain length is followed successively by diethylenetriamine, triethylene tetramine, TEPA, five ethene by short and length Hexamine, the amine of six ethene seven, the amine of seven ethene eight.
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| RU2496571C1 (en) * | 2012-03-15 | 2013-10-27 | Закрытое Акционерное общество Научно-технический центр "БиАСеп" (ЗАО НТЦ "БиАСеп") | Anion-exchange sorbent for simultaneous ion chromatographic determination of polarisable and non-polarisable inorganic anions and method for production thereof |
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